Crystallogenetic models for metasomatic replacement in zircons: implications for U–Pb geochronology of Precambrian rocks

Recrystallization of zircons under the influence of fluids was studied using examples from Precambrian rocks (microcline granites, metasedimentary, and mafic rocks) of the Kola Peninsula. All zircon crystals showed complex internal textures visible by cathodoluminescence and backscattered electron (BSE) imaging. Detailed mineralogical and geochemical studies with subsequent secondary ion mass spectrometer U–Pb dating of different zircon domains show that secondary texture formation can be interpreted in terms of metasomatic replacement of zircon crystals on the base of crystallogenetic experimental models. Mechanisms of zircon replacement and interpretation of U–Pb ages for secondary zircon domains are dependent on the degree of damage of the zircon structure and the fluid composition. The recrystallization of metamict zircon without additional supply of new zircon substance (Zr, SiO₂) goes with the dissolution of amorphous domains and precipitation of new polycrystalline zircon, which preserves the U–Pb initial age, but loses radiogenic lead, and the lower intercept of Discordia lines with the Concordia curve determines the time of fluid influence. The recrystallization of metamict zircon or crystalline zircon with high contents of impurities with additional supply of Si and Zr forms monocrystalline replacements. Dissolution of primary zircon is accompanied by growth of new zircon domains differing in the composition of isomorphic impurities and zones of transitional composition, whose ages have no geological sense. The study is of particular importance for zircons from Precambrian rocks with long and complex histories.     

变质岩中锆石U—Pb计时问题评述——兼论大别造山带锆石定年

锆石是U－Pb计时的首选对象，对于地质历史复杂的变质岩地区，如大别碰撞造山带的年代学研究，具有不可替代的重要性。变质岩中锆石经历了Pb的扩散丢失作用；晶格损伤导致的蜕晶化作用；增生－混合作用和重结晶作用。这些过程对锆石计时的准确性和有效性带来不同程度的影响。为了使测定的年龄有确定的地质意义，在进行锆石U－Pb定年前，必需对锆石进行成因矿物学和矿物内部结构研究，特别是阴极荧光和背散射电子成像研究，通过内部结构特征确定锆石成因过程。在化学U－Pb法定年时注意普通铅校正和^204Pb测定值对年龄的影响，尽量选择单一成因锆石。特别强调在大别造山带年代学中引入锆石微区离子探针定年技术。     

Grain-scale variations in trace element composition of fluid-altered zircon,Acasta Gneiss Complex,northwestern Canada

SEM back-scattered electron images of zircon separates from a 2.9 Ga granitic dyke from the Acasta Gneiss Complex, Slave Province, reveal primary igneous oscillatory zoning which is transgressively overprinted by irregular alteration domains. Electron microprobe analyses show that altered zircon domains are depleted in Zr and Si relative to unaltered zircon while retaining a constant Zr/Si ratio. SIMS trace element analyses indicate that LREE are preferentially enriched in the altered domains. Altered zircon contains elevated concentrations of Ba (up to 580 ppm), Ca (up to 2% weight of the element) and common Pb (>50 ppb). The presence of LREE, Ca, Ba and common Pb in the zircons is interpreted to be the result of secondary alteration by an aqueous fluid, and not by primary incorporation during crystallization. We propose that the alteration-related elements are located in amorphous zircon domains.     

Small-angle X-ray scattering measurement of the internal microstructure of natural zircon crystals

Zircon crystals change their physical properties significantly over time in response to the radiation damage (metamictization) induced in the lattice by the presence of radionuclides U and Th. Crystalline zircon has extremely low diffusion rates of the radiogenic daughter product, Pb. Lead diffusion is enhanced in metamict volumes, but the observed lack of correlation between Pb loss and metamictization in natural zircons requires that other mechanisms control the incidence of Pb migration. The proposition that self-induced stress and elasticity contrasts in zoned natural crystals create fast-track Pb migration pathways, in response to time-integrated radiation damage, requires a means of detecting the microstructures within zircons at the interatomic scale at which Pb migration takes place. Small-angle X-ray scattering (SAXS) is introduced as a means of detecting candidate microstructures including subgrain boundaries, defect networks and microfractures produced by differential metamictization. It is shown that a classical X-ray source yields measurable SAXS response from contrasting metamict and crystalline domains within a crystal, and these properties are quantified for a metamict zircon megacryst. Detection of the weaker SAXS response expected from microfractures and networked defects requires the more intense X-rays of synchrotron-source radiation.     

Zircon response to high-grade metamorphism as revealed by U–Pb and cathodoluminescence studies

Correct interpretation of zircon ages from high-grade metamorphic terrains poses a major challenge because of the differential response of the U–Pb system to metamorphism, and many aspects like pressure–temperature conditions, metamorphic mineral transformations and textural properties of the zircon crystals have to be explored. A large (c. 450?km²) coherent migmatite complex was recently discovered in the Bohemian Massif, Central European Variscides. Rocks from this complex are characterized by granulite- and amphibolite-facies mineral assemblages and, based on compositional and isotopic trends, are identified as the remnants of a magma body derived from mixing between tonalite and supracrustal rocks. Zircon crystals from the migmatites are exclusively large (200–400?μm) and yield ²⁰⁷Pb/²⁰⁶Pb evaporation ages between 342–328?Ma and single-grain zircon fractions analysed by U–Pb ID-TIMS method plot along the concordia curve between 342 and 325?Ma. High-resolution U–Pb SHRIMP analyses substantiate the existence of a resolvable age variability and yield older ²⁰⁶Pb/²³⁸U ages (342–330?Ma, weighted mean age?=?333.6?±?3.1?Ma) for inner zone domains without relict cores and younger ²⁰⁶Pb/²³⁸U ages (333–320?Ma, weighted mean age?=?326.0?±?2.8?Ma) for rim domains. Pre-metamorphic cores were identified only in one sample (²⁰⁶Pb/²³⁸U ages at 375.0?±?3.9, 420.3?±?4.4 and 426.2?±?4.4?Ma). Most zircon ages bracket the time span between granulite-facies metamorphism in the Bohemian Massif (~345?Ma) and the late-Variscan anatectic overprint (Bavarian phase, ~325?Ma). It is argued that pre-existing zircon was variously affected by these metamorphic events and that primary magmatic growth zones were replaced by secondary textures as a result of diffusion reaction processes and replacement of zircon by dissolution and recrystallization followed by new zircon rim growth. Collectively, the results show that the zircons equilibrated during high-grade metamorphism and record partial loss of radiogenic Pb during post-peak granulite events and new growth under subsequent anatectic conditions.     

Recrystallisation of oscillatory zoned zircon: some geochronological and petrological implications

Oscillatory zoning is a common feature in zircons from acid igneous rocks and is believed to form during crystallisation of zircons from a magma by a mechanism which is not yet understood. Many zircons with oscillatory zoning also show a patchwork replacement of zoned by unzoned zircon. The unzoned zircon occurs as rounded, transgressive patches distributed throughout the zoned zircon and as areas of transitional replacement where zoned zircon is progressively replaced by unzoned zircon such that only faint traces of original zones remain. This structure is interpreted as a progressive recrystallisation of the oscillatory zoned zircon made unstable by the incorporation of high concentrations of contaminant elements during magmatic crystallisation. Recrystallisation overprints oscillatory zones and appears to have occurred after completion of primary crystallisation. It is accompanied by loss of U, Th and Pb and the removal of oscillatory zones. The recrystallised unzoned zircon is extremely stable with respect to later Pb loss and tends to retain a concordant or slightly discordant U–Pb age. Recrystallisation provides a mechanism for resetting zircon U–Pb ages which is independent of the degree of radiation damage of the zircon lattice. This differs from other models of discordance which involve a leaching of radiogenic Pb as a consequence of a progressive breakdown of the zircon structure through time-integraded radiation damage further enhanced by high concentrations of trace-element contaminants. The U–Pb age of the unzoned zircon may date the recrystallisation event, which may be close to the age of primary crystallisation or reflect a later metamorphism.Dedicated to Borwin Grauert on the occasion of his sixtieth birthday     

Response of Precambrian zircon to the chemical abrasion (CA-TIMS) method and implications for improvement of age determinations

Electron backscatter imaging, Raman spectroscopy and U-Pb geochronology have been applied to Precambrian zircon grains that were annealed at 1000 and 1450 °C for various times, then leached with HF to constrain the conditions for healing radiation damage and attaining primary U-Pb zircon ages using the chemical abrasion (CA-TIMS) method. SEM images reveal a variety of textures for ZrO₂ overgrowths on 1450 °C annealed and leached zircon surfaces that depend on the degree of radiation damage and annealing history. Highly damaged zircon produces finer textures than zircon with less damage.Raman spectroscopy indicates that crystals with different levels of radiation damage are only partially restored by annealing at 1000 °C for 2-3 days. Longer annealing periods of 20 days are not noticeably more effective. Annealing at 1450 °C for 1 h results in partial breakdown of zircon but restores Raman peak widths and wave numbers to values characteristic of undamaged zircon after ZrO₂ overgrowths are removed by HF. Raman spectra are much less sensitive to polarization angle for annealed highly damaged grains than for weakly damaged zircon.U-Pb isotopic analyses of low to moderately damaged zircon (alpha fluence ranging up to 10¹⁹/g corresponding to an amorphization volume fraction of 80% or more) yield almost concordant data (0.3-0.5% discordance) after high-temperature annealing at 1450 °C followed by HF leaching at 195 °C. Analyses of cracked zircon annealed at 1450 °C and leached may remain discordant but those of uncracked grains are concordant. Most analyses show primary ²⁰⁷Pb/²⁰⁶Pb ages although cracked grains annealed at 1450 °C may produce discordant data with ²⁰⁷Pb/²⁰⁶Pb ages that are too young after leaching. The solubility of highly damaged, very disordered zircon (amorphization level of 99%) is only slightly reduced by annealing, and analyses of leach residues are strongly discordant although primary ²⁰⁷Pb/²⁰⁶Pb ages are obtained.Annealing of highly damaged zircon under any conditions apparently results in a mass of randomly oriented micro-crystals that pseudomorph the original grain. This could explain the fine-scale pattern observed on etched crystal surfaces, reduced anisotropy at the 5 μm scale of the Raman laser beam and high solubility in HF. It may be impossible to restore primary U-Pb isotopic ages in such cases but precise ages can still potentially be determined from ²⁰⁷Pb/²⁰⁶Pb ratios or by application of the air abrasion method.     

A study of complex discordance in zircons using step-wise dissolution techniques

Step-wise dissolution techniques applied to a variety of zircon samples, including those with combined inheritance plus later isotopic disturbance, reveal both the complexity of zircon isotopic systematics, and successfully “see through” this complexity to extract high-quality age information. The chemical procedures for the partial dissolution steps must be designed to extract completely all the U and Pb associated with the zircon digested in each step, in order to avoid large, laboratory-induced fluctuations in U/Pb ratio from step to step. In general, relatively short initial partial dissolution steps remove disturbed zircon domains characterized by very high U concentrations and low ²⁰⁶Pb/²³⁸U ages. In some cases the initial step yields the lowest ²⁰⁶Pb/²³⁸U age, reflecting both the high accessibility and solubility of the most disturbed domains. In other cases, disturbed domains evidently reside deep within the zircons, and are attacked only when the second or third steps penetrate to the interior via cracks or flaws to “mine out” these domains. In all the samples in this study, and regardless of the details of the steps, about a week of digestion time at 80°C removed most of the highly disturbed domains, leaving further partial dissolution steps and/or the total digestion of the final residue to sample highly refractory (i.e., highly insoluble), relatively low U zircon domains. The early partial digestion steps also remove virtually all the common Pb associated with the zircons. Study of partially digested zircons by scanning electron microscope reveals that at least in part, the disturbed, high-U, highly soluble domains and the less (un-?) disturbed, low-U, highly refractory domains are defined by primary igneous zoning on a micron or even sub-micron scale, well below the resolution of the “SHRIMP”, for example. In the case of zircons lacking any inheritance, the residue analyses yield near-concordant, highly precise results. In the case of zircons with inherited components, the residue analyses appear to plot on “primary” discordia lines. Depending on the relative solubility of the inherited versus the igneous component, the final residue will concentrate one or the other.     

Enhanced diffusion of Uranium and Thorium linked to crystal plasticity in zircon

The effects of crystal-plasticity on the U-Th-Pb system in zircon is studied by quantitative microstructural and microchemical analysis of a large zircon grain collected from pyroxenite of the Lewisian Complex, Scotland. Electron backscatter diffraction (EBSD) mapping reveals a c.18° variation in crystallographic orientation that comprises both a gradual change in orientation and a series of discrete low-angle (<4°) boundaries. These microstructural data are consistent with crystal-plastic deformation of zircon associated with the formation and migration of dislocations. A heterogeneous pattern of dark cathodoluminescence, with the darkest domains coinciding with low-angle boundaries, mimics the deformation microstructure identified by EBSD. Geochemical data collected using the Sensitive High Resolution Ion MicroProbe (SHRIMP) shows a positive correlation between concentrations of the elements U, Th and Pb (ranging from 20–60 ppm, 30–110 ppm, and 14–36 ppm, respectively) and Th/U ratio (1.13 – 1.8) with the deformation microstructure. The highest measured concentrations and Th/U coincide with low-angle boundaries. This enrichment is interpreted to reflect enhanced bulk diffusion of U and Th due to the formation and migration of high-diffusivity dislocations. ²⁰⁷Pb/²⁰⁶Pb ages for individual analyses show no significant variation across the grain, and define a concordant, combined mean age of 2451 ± 14 Ma. This indicates that the grain was deformed shortly after initial crystallization, most probably during retrograde Inverian metamorphism at amphibolite facies conditions. The elevated Th over U and consistent ²⁰⁷Pb/²⁰⁶Pb ages indicates that deformation most likely occurred in the presence of a late-stage magmatic fluid that drove an increase in the Th/U during deformation. The relative enrichment of Th over U implies that Th/U ratio may not always be a robust indicator of crystallization environment. This study provides the first evidence of deformation-related modification of the U-Th system in zircon and has fundamental implications for the application and interpretation of zircon trace element data.     

Alteration of crystalline zircon solid solutions: a case study on zircon from an alkaline pegmatite from Zomba–Malosa, Malawi

A natural, altered zircon crystal from an alkaline pegmatite from the Zomba–Malosa Complex of the Chilwa Alkaline Province in Malawi has been studied by a wide range of analytical techniques to understand the alteration process. The investigated zircon shows two texturally and chemically different domains. Whereas the central parts of the grain (zircon I) appear homogeneous in backscattered electron images and are characterised by high concentrations of trace elements, particularly Th, U, and Y, the outer regions (zircon II) contain significantly less trace elements, numerous pores, and inclusions of thorite, ytttrialite, and fergusonite. Zircon II contains very low or undetectable concentrations of non-formula elements such as Ca, Al, and Fe, which are commonly observed in high concentrations in altered radiation-damaged zircon. U–Pb dating of both zircon domains by LA-ICPMS and SHRIMP yielded statistically indistinguishable U–Pb weighted average ages of 119.3 ± 2.1 (2σ) and 118 ± 1.2 (2σ) Ma, respectively, demonstrating that the zircon had not accumulated a significant amount of self-irradiation damage at the time of the alteration event. Electron microprobe dating of thorite inclusions in zircon II yielded a Th–U-total Pb model age of 122 ± 5 (2σ) Ma, supporting the age relationship between both zircon domains. The hydrothermal solution responsible for the alteration of the investigated zircon was alkaline and rich in CO₃ ²⁻, as suggested by the occurrence of REE carbonates and CO₂-bearing fluid inclusions. The alteration of the crystalline, trace element-rich zircon is explained by an interface-coupled dissolution-reprecipitation mechanism. During such a process, the congruent dissolution of the trace element-rich parent zircon I was spatially and temporally coupled to the precipitation of the trace element-poor zircon II at an inward moving dissolution-precipitation front. The driving force for such a process was merely the difference between the solubility of the trace element-rich and -poor zircon in the hydrothermal solution. The replacement process and the occurrence of mineral inclusions and porosity in the product zircon II is explained by the thermodynamics of solid solution-aqueous solution systems.     

Alpha-recoil in U–Pb geochronology: effective sample size matters

Displacement of the daughter isotope by a-recoil results in an open system on the nanoscale. For a heterogeneous distribution of U and Th, this redistribution of intermediate and stable daughter isotopes results in subvolumes with a deficit of Pb and others with an excess of Pb. Whether such heterogeneities affect the analyzed U–Pb system depends on: (1) the volume of the analyzed sample, (2) the degree and scale of heterogeneity in the U and Th distribution, and (3) the analytical procedure. Spatial separation of parent and daughter through a-recoil affects the U–Pb systematics of leached samples, where leaching gives access to domains less than 1 µm wide. Anomalous data patterns originating from recoil induced parent-to-daughter fractionation are more important if there are strong heterogeneities in the U and Th distribution, whereby Pb excess appears more pronounced than Pb deficit. Fractionation of parent and daughter elements through selective dissolution of U-REE-rich growth zones in zircon and U-inclusions in columbite, as well as the presence of U–Th-rich micro-inclusions in silicates dated using a step-leaching scheme, may result in anomalous ²⁰⁷Pb _rad/ ²⁰⁶Pb _rad, scattered ²⁰⁶Pb _rad/ ²³⁸U and ²⁰⁷Pb _rad/ ²³⁵U, and reverse discordance. The accumulated structural damage controls the leaching and dissolution behavior, but may also influence the non-stoichiometric element mobilization during sputtering or ablation in the analysis of U-rich samples by SHRIMP and LA-MC-ICP-MS.     

Interpretation of discordant U-Pb zircon ages: An evaluation

The most widely used technique for the determination of high precision mineral growth ages in igneous and metamorphic rocks is dating of zircons with the U-Pb method. The interpretation of these ages, particularly in metamorphic settings, is hampered by an incomplete understanding of the common phenomenon of partial Pb-loss in zircon. In principle, this Pb-loss may occur in four very different ways: diffusion in metamict zircon, diffusion in pristine zircon, leaching from metamict zircon and recrystallization of metamict zircon. Here it is argued that, under conditions common in the continental crust, Pb-loss is only possible in partially to strongly metamict zircons. Pb-diffusion in the pristine zircon lattice is insignificant up to temperatures of at least 1000 °C. Pb-loss is only possible if the zircons experienced a time interval below their annealing temperature of about 600–650 °C, because only below this temperature can the lattice damage through α-decay and spontaneous fission accumulate. Zircons that remain above this temperature do not lose Pb by diffusion and will stay closed systems. Complete resetting of the U-Pb system in zircon under crustal conditions is only possible through dissolution and reprecipitation of zircon. Partial resetting results from recrystallization, leaching or diffusion in metamict zircon. As a consequence, special care has to be taken to interpret lower intercepts on concordia diagrams defined by discordant U-Pb data. Lower intercept ages may be significant only if they are defined by zircons with low U-content (<100 p.p.m.) or if confirmed by other geochronological methods. In addition, the accuracy of the lower intercept should be confirmed by abrading the zircon fractions that define the discordia.     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.     

Determination of the oxidation state of radiogenic Pb in natural zircon using X-ray absorption near-edge structure

We examined the L_III-edge Pb X-ray absorption near-edge structure (XANES) of three natural zircon samples with different amounts of radiation doses (1.9 × 10¹⁵ to 6.8 × 10¹⁵ α-decay events/mg). The results suggest that the oxidation state of radiogenic Pb in the zircon sample with the highest radiation dose is divalent. The XANES spectra of the two other samples with lower radiation doses suggest that radiogenic Pb(II) is present, and further that some Pb may be tetravalent. This is the first work on the determination of the oxidation state of radiogenic Pb in natural zircon using XANES.     

Microstructure of 24-1928 Ma concordant monazites; implications for geochronology and nuclear waste deposits

The microstructure of monazite was studied using scanning electron microscopy (SEM), electron microprobe analysis (EMP), X-ray diffraction patterns (XRD), and transmission electron microscopy (TEM). Four well-characterized monazites were investigated, having very different concordant U-Pb ages (24 to 1928 Ma), and up to ∼15 wt.% ThO₂, and ∼0.94 wt. % UO₂. The SEM and EMP analyses of polished single crystal fragments reveal the absence of significant chemical zoning. XRD and TEM investigations show that the monazites are not metamict, despite their old ages, very high abundances of radionuclides, and hence, high time-integrated radiation doses. Except for the youngest one, the monazite crystals are composed of a mosaic of crystalline but slightly distorted domains. This structure is responsible for the presence of (1) mottled diffraction contrasts on the TEM, and (2) a second structural phase (B), with very broad reflections in the XRD patterns. Older monazites receive higher self-irradiation doses, and hence, they contain higher amounts of this B-phase. For the 1928 Ma monazite, XRD reveals only the broad reflections of phase B, implying that the whole monazite was affected by radiation damage that resulted in total distortion of the lattice. It is concluded that radiation damage in the form of amorphous domains does not accumulate in monazite because self-annealing heals the defects as they are produced by α-decay damage. The only memory of irradiation-induced defects is the presence of distorted domains. As the diffusion rate of Pb in an undisturbed monazite lattice is extremely low, Pb loss due to volume diffusion out of the monazite lattice is virtually impossible. This is considered as one reason why almost all monazites have concordant U-Th-Pb ages. Moreover, as long-term self-irradiation effects are limited in monazite, we consider this phase as a good candidate for the storage of high-level nuclear waste under the aspect of its high resistance to irradiation.     

Contrasting response of monazite and zircon to a high-T thermal overprint

Contact metamorphism in the aureole of the 1322 Ma Makhavinekh Lake Pluton, northern Labrador, affected monazite and zircon in the adjacent 1850 Ma metapelitic gneisses. Transformation of regional garnet and sillimanite to lower-pressure symplectitic intergrowths of cordierite, orthopyroxene, and spinel was accompanied by resorption of inherited monazite inclusions in garnet coupled with the appearance of coronitic high-Y monazite rims. In situ ion-microprobe dating is used to show that high-Y rims formed during contact metamorphism. Liberation of Y and HREE from garnet also gave rise to new xenotime growth. The coronitic nature of monazite overgrowths reflects the diffusion-controlled nature of net-transfer reactions whereas its higher Y composition reflects equilibration with xenotime at peak T (> 800 °C) conditions in the inner aureole. Very thin overgrowths on inherited zircon were also encountered, but only where zircon is surrounded by the symplectitic assemblage, reflecting liberation of Zr from garnet. Although these overgrowths are too thin to date using conventional ion-microprobe techniques, well-developed triple junctions between zircon and orthopyroxene suggests that they grew in textural equilibrium with the contact metamorphic assemblage.

In contrast to monazite, inherited zircon remained intact during contact metamorphism, exhibiting no change in morphology (other than the growth of thin rims) or internal zoning throughout the aureole. However, inherited sector-zoned zircons of anatectic origin display evidence for intracrystalline Pb redistribution in the inner aureole. In these samples, ion-microprobe analyses encountered heterogeneous Pb signals and a dispersion of ²⁰⁷Pb / ²⁰⁶Pb dates away from the well constrained 1850 Ma age of regional metamorphism. Whereas analyses from the outer aureole faithfully record the age of regional metamorphism, those from the inner aureole are normally and reversely discordant and distributed along a line collinear with a 1850 to 1322 Ma discordia. This disturbance is correlated with proximity to the pluton implying that Pb was mobile in the zircon lattice during contact metamorphism. Most grains are characterized by apparent Pb loss from low-U domains and apparent Pb gain in higher-U domains. These data are interpreted to reflect recovery of strained crystalline domains leading to expulsion of Pb* that was able to efficiently diffuse into higher-U domains that were partly amorphous prior to rapid reheating in the inner aureole.     

In situ U–Pb dating and trace element analysis of zircons in thin sections of eclogite: Refining constraints on the ultra high-pressure metamorphism of the Sulu terrane,China

In situ U–Pb dating and trace element analysis of zircons, combined with a textural relationship investigation in thin section, is a powerful tool to constrain the ultra high-pressure stage of high-grade metamorphism. Two types of zircon grains have been identified in thin sections of a retrograde eclogite from the main hole of the Chinese Continental Scientific Drill project in the Sulu UHP terrane. Type 1 zircon grains occur as inclusions in fresh garnet and omphacite, and Type 2 zircon grains were found in symplectite around omphacite. The fresh rims of Type 1 zircons and mantles of a few Type 2 zircons exhibit remarkably lower REE, Y, Nb and Ta contents than the inherited zircon cores, suggesting coeval growth with garnet, rutile and apatite during UHP metamorphism. These may have formed in the UHP metamorphism and survived retrograde metamorphism. The weighted average ²⁰⁶Pb/²³⁸U age of these zircon domains (230 ± 4 Ma, 2σ) agrees well with the published age of coesite-bearing zircon separates (230 ± 1 Ma, 2σ), suggesting that the peak UHP metamorphism in the Sulu terrane may have occurred at ~ 230 Ma.Zircon domains surrounded or cut across by symplectite could have been altered by retrograde metamorphism. Together, they provide a younger weighted average ²⁰⁶Pb/²³⁸U age of 209 ± 4 Ma (2σ). These retrograde zircon domains have similar REE compositions to the ~ 230 Ma UHP zircon domains. These observations imply that the ~ 209 Ma zircon domains could have formed by fluid activity-associated alterations in the amphibolite-facies metamorphism, which could have resulted in the complete loss of Pb but not REEs in these domains.     

Decoding a protracted zircon geochronological record in ultrahigh temperature granulite,and persistence of partial melting in the crust,Rogaland, Norway

This contribution evaluates the relation between protracted zircon geochronological signal and protracted crustal melting in the course of polyphase high to ultrahigh temperature (UHT; T?>?900 °C) granulite facies metamorphism. New U–Pb, oxygen isotope, trace element, ion imaging and cathodoluminescence (CL) imaging data in zircon are reported from five samples from Rogaland, South Norway. The data reveal that the spread of apparent age captured by zircon, between 1040 and 930 Ma, results both from open-system growth and closed-system post-crystallization disturbance. Post-crystallization disturbance is evidenced by inverse age zoning induced by solid-state recrystallization of metamict cores that received an alpha dose above 35 × 10¹⁷ α  g^?1. Zircon neocrystallization is documented by CL-dark domains displaying O isotope open-system behaviour. In UHT samples, O isotopic ratios are homogenous (δ¹⁸O = 8.91?±?0.08‰), pointing to high-temperature diffusion. Scanning ion imaging of these CL-dark domains did not reveal unsupported radiogenic Pb. The continuous geochronological signal retrieved from the CL-dark zircon in UHT samples is similar to that of monazite for the two recognized metamorphic phases (M1: 1040–990 Ma; M2: 940–930 Ma). A specific zircon-forming event is identified in the orthopyroxene and UHT zone with a probability peak at ca. 975 Ma, lasting until ca. 955 Ma. Coupling U–Pb geochronology and Ti-in-zircon thermometry provides firm evidence of protracted melting lasting up to 110 My (1040–930 Ma) in the UHT zone, 85 My (ca. 1040–955 Ma) in the orthopyroxene zone and some 40 My (ca. 1040–1000 Ma) in the regional basement. These results demonstrate the persistence of melt over long timescales in the crust, punctuated by two UHT incursions.     

The youngest basic oceanic magmatism in the Alps (Late Cretaceous<Emphasis Type="Italic">;</Emphasis> Chiavenna unit,Central Alps): geochronological constraints and geodynamic significance

Cathodoluminescence-controlled radiometric dating (U–Pb SHRIMP) was carried out on zircon domains from metabasic rocks of the Chiavenna unit, a major mafic/ultramafic-bearing unit in the Central Alps. Co-magmatic zircon domains from amphibolites near Chiavenna and Prata areas yielded weighted mean ²⁰⁶Pb/²³⁸U ages at 93.0±2.0 and 93.9±1.8 Ma, respectively, interpreted as the age of crystallization of the magmatic protoliths. These ages fit well with the time of late spreading in the Valais Ocean, as suggested by previous paleogeographic reconstructions. Inherited zircon grains and/or core domains (Permo-Triassic, Carboniferous, Proterozoic) are abundant, indicating proximity of the Chiavenna unit to thinned continental crust. This is in line with the origin of this unit from subcontinental mantle sources, as suggested previously on petrological and structural grounds. Metamorphic zircon domains from one amphibolite near Chiavenna yielded a weighted mean ²⁰⁶Pb/²³⁸U age at 37.1±0.9 Ma, identical to the 38.5±0.9 Ma SHRIMP age of an amphibolitized eclogite of the Antrona ophiolites (Valais domain, Western Alps). Precise metamorphic ages were difficult to obtain from the composite (poly)metamorphic rim domains of the Prata amphibolite. This is attributed to the location of the Prata area close to the granulite-facies Gruf unit (metamorphosed at ca. 33 Ma) and to the 24–25 Ma old Novate granite, where metamorphic/fluid events probably caused multiple resetting to various degrees. The ca. 93 Ma old magmatism, identified for the first time in the Chiavenna unit, is the youngest basic oceanic magmatism reported in the Alps. The 37.1±0.9 Ma old metamorphism in the Chiavenna unit, attributed to the Valais domain, confirms the model suggesting stepwise younging of metamorphic ages from the south (Adriatic plate) to the north (European plate). It is older than metamorphism in the European margin (ca. 35–31 Ma) lying to the north of the Valais domain and younger than that in the Piemont–Ligurian Ocean (ca. 44–45 Ma) lying to the south of the Valais domain.Editorial responsibility: W. Schreyer     

扬子地块西南缘大红山群老厂河组变质火山岩的锆石U-Pb定年及其地质意义

大红山群是扬子地台西缘相对较老的地层单元,普遍经历了绿片岩相-低角闪岩相变质作用。其中部的曼岗河组、红山组已获得古元古代晚期～1.68Ga的成岩年龄,其底部的老厂河组却未有相关年龄的报道。大红山群的变质时代目前也无精确的年龄结果。本文以老厂河组厚层变质沉积岩中的薄层变质火山岩样品为研究对象,在岩相学研究的基础上,运用LA-ICP-MS方法对变质火山岩锆石进行原位U-Pb同位素定年及相关的微量、稀土元素测试,获得变质火山岩的原岩年龄和变质年龄:(1)老厂河组变质中酸性岩和变质基性岩中岩浆锆石微区的207Pb/206Pb加权平均年龄分别为1711±4Ma和1686±4Ma,限定老厂河组的形成年龄范围为1711～1686Ma;(2)变质基性岩(石榴斜长角闪岩)中变质锆石的206Pb/238U年龄为849±12Ma。本文结果表明,大红山群的形成时代可提早至1711±4Ma,又一次证明了扬子地台西缘古老结晶基底的存在;大红山群在～850Ma经历了一期新元古代变质事件,这期变质可能是与扬子地台西缘新元古代岩浆事件有关的区域变质事件。