Relationship among titanium,rare earth elements,U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.     

Quantitative characterization of plastic deformation of zircon and geological implications

The deformation-related microstructure of an Indian Ocean zircon hosted in a gabbro deformed at amphibolite grade has been quantified by electron backscatter diffraction. Orientation mapping reveals progressive variations in intragrain crystallographic orientations that accommodate 20° of misorientation in the zircon crystal. These variations are manifested by discrete low-angle (<4°) boundaries that separate domains recording no resolvable orientation variation. The progressive nature of orientation change is documented by crystallographic pole figures which show systematic small circle distributions, and disorientation axes associated with 0.5–4° disorientation angles, which lie parallel to rational low index crystallographic axes. In the most distorted part of the grain (area A), this is the [100] crystal direction. A quaternion analysis of orientation correlations confirms the [100] rotation axis inferred by stereographic inspection, and reveals subtle orientation variations related to the local boundary structure. Microstructural characteristics and orientation data are consistent with the low-angle boundaries having a tilt boundary geometry with dislocation line [100]. This tilt boundary is most likely to have formed by accumulation of edge dislocations associated with a 〈001〉{100} slip system. Analysis of the energy associated with these dislocations suggest they are energetically more favorable than TEM verified 〈010〉{100} slip. Analysis of minor boundaries in area A indicates deformation by either (001) edge, or [100](100) and [001](100) screw dislocations. In other parts of the grain, cross slip on (111), and (112) planes seems likely. These data provide the first detailed microstructural analysis of naturally deformed zircon and indicate ductile crystal-plastic deformation of zircon by the formation and migration of dislocations into low-angle boundaries. Minimum estimates of dislocation density in the low-angle boundaries are of the order of ∼3.10¹⁰ cm⁻². This value is sufficiently high to have a marked effect on the geochemical behavior of zircon, via enhanced bulk diffusion and increased dissolution rates. Therefore, crystal plasticity in zircon may have significant implications for the interpretation of radiometric ages, isotopic discordance and trace element mobility during high-grade metamorphism and melting of the crust.     

Detrital zircon ages from southern Norway – implications for the Proterozoic evolution of the southwestern Baltic Shield

An ion-microprobe (SIMS) U-Pb zircon dating study on four samples of Precambrian metasediments from the high-grade Bamble Sector, southern Norway, gives the first information on the timing of discrete crust-forming events in the SW part of the Baltic Shield. Recent Nd and Pb studies have indicated that the sources of the clastic metasediments in this area have crustal histories extending back to 1.7 to 2.1 Ga, although there is no record of rocks older than 1.6 Ga in southern Norway. The analysed metasediments are from a sequence of intercalated, centimetre to 10-metre wide units of quartzites, semi-metapelites, metapelites and mafic granulites. The zircons can be grouped in two morphological populations: (1) long prismatic; (2) rounded, often flattened. The BSE images reveal that both populations consist of oscillatory zoned, rounded and corroded cores (detrital grains of magmatic origin), surrounded by homogeneous rims (metamorphic overgrowths). The detrital zircons have ²⁰⁷Pb/²⁰⁶Pb ages between 1367 and 1939 Ma, with frequency maxima in the range 1.85 to 1.70 Ga and 1.60 to 1.50 Ga. There is no correlation between crystal habit and age of the zircon. One resorbed, inner zircon core in a detrital grain is strongly discordant and gives a composite inner core-magmatic outer core ²⁰⁷Pb/²⁰⁶Pb age of 2383 Ma. Two discrete, unzoned zircons have ²⁰⁷Pb/²⁰⁶Pb ages of 1122 and 1133 Ma, representing zircon growth during the Sveconorwegian high-grade metamorphism. Also the μm wide overgrowths, embayments in the detrital cores and apparent “inner cores” which represent secondary metamorphic zircon growth in deep embayments in detrital grains, are of Sveconorwegian age. The composite-detrital-metamorphic zircon analyses give generally discordant ²⁰⁶Pb/²³⁸U versus ²⁰⁷Pb/²³⁵U ratios and maximum ²⁰⁷Pb/²⁰⁶Pb ages of 1438 Ma. These data demonstrate the existence of a protocrust of 1.7 to 2.0 Ga in the southwestern part of the Baltic Shield, implying a break in the overall westward younging trend of the Precambrian crust, inferred from the southeastern part of the Baltic Shield. Received: 8 April 1997 / Accepted: 14 July 1997     

U–Pb systematics of the McClure Mountain syenite: thermochronological constraints on the age of the 40Ar/39Ar standard MMhb

Recent advances in U–Pb geochronology allow unprecedented levels of precision in the determination of geological ages. However, increased precision has also illuminated the importance of understanding subtle sources of open-system behavior such as Pb-loss, inheritance, intermediate daughter product disequilibria, and the accuracy of the model assumptions for initial Pb. Deconvolution of these effects allows a much richer understanding of the power and limitations of U–Pb geochronology and thermochronology. In this study, we report high-precision ID-TIMS U–Pb data from zircon, baddelleyite, titanite and apatite from the McClure Mountain syenite, from which the ⁴⁰Ar/³⁹Ar hornblende standard MMhb is derived. We find that excess ²⁰⁶Pb in zircon due to inclusions of high-Th minerals and elevated Th/U in titanite and apatite jeopardize the utility of the ²³⁸U–²⁰⁶Pb system in this rock. Strongly air-abraded zircons give dates that are younger than chemical-abraded zircons, which yield a statistically robust ²⁰⁷Pb/²³⁵U date of 523.98±0.12 Ma that is interpreted as the crystallization age. We explore the best method of Pb_c correction in titanite and apatite by analyzing the U–Pb isotopes of K-feldspar and using 2-D and 3-D regression methods—the latter of which yields the best results in each case. However, the calculated compositions of Pb_c for titanite, apatite and K-feldspar are different, implying that using a single Pb_c correction for multiple U–Pb thermochronometers may be inaccurate. The U–Pb thermochronological results are used to predict a closure time for Ar in hornblende of 522.98±1.00 Ma. Widely cited K–Ar and ⁴⁰Ar/³⁹Ar dates overlap with the U–Pb date, and relatively large errors make it impossible to verify whether U–Pb dates are systematically ≤1% older than K–Ar and ⁴⁰Ar/³⁹Ar dates.     

U–Pb isotopic dating of titanite microstructures: potential implications for the chronology and identification of large impact structures

Identifying and dating large impact structures is challenging, as many of the traditional shock indicator phases can be modified by post-impact processes. Refractory accessory phases, such as zircon, while faithful recorders of shock wave passage, commonly respond with partial U–Pb age resetting during impact events. Titanite is an accessory phase with lower Pb closure temperature than many other robust chronometers, but its potential as indicator and chronometer of impact-related processes remains poorly constrained. In this study, we examined titanite grains from the Sudbury (Ontario, Canada) and Vredefort (South Africa) impact structures, combining quantitative microstructural and U–Pb dating techniques. Titanite grains from both craters host planar microstructures and microtwins that show a common twin–host disorientation relationship of 74° about <102>. In the Vredefort impact structure, the microtwins deformed internally and developed high- and low-angle grain boundaries that resulted in the growth of neoblastic crystallites. U–Pb isotopic dating of magmatic titanite grains with deformation microtwins from the Sudbury impact structure yielded a ²⁰⁷Pb/²⁰⁶Pb age of 1851?±?12 Ma that records either the shock heating or the crater modification stage of the impact event. The titanite grains from the Vredefort impact structure yielded primarily pre-impact ages recording the cooling of the ultra-high-temperature Ventersdorp event, but domains with microtwins or planar microstructures show evidence of U–Pb isotopic disturbance. Despite that the identified microtwins are not diagnostic of shock-metamorphic processes, our contribution demonstrates that titanite has great potential to inform studies of the terrestrial impact crater record.     

U–Pb geochronology of gneisses and granitoids from the Danish island of Bornholm: new evidence for 1.47–1.45 Ga magmatism at the southwestern margin of the East European Craton

The Danish island of Bornholm is located at the southwestern margin of the Fennoscandian Shield, and features exposed Precambrian basement in its northern and central parts. In this paper, we present new U–Pb zircon and titanite ages for granites and orthogneisses from 13 different localities on Bornholm. The crystallization ages of the protolith rocks all fall within the range 1,475–1,445 Ma (weighted average ²⁰⁷Pb/²⁰⁶Pb ages of zircon). Minor age differences, however, may imply a multi-phase emplacement history of the granitoid complex. The presence of occasional inherited zircons (with ages of 1,700–1,800 Ma) indicates that the Bornholm granitoids were influenced by older crustal material. The east–west fabric observed in most of the studied granites and gneisses, presumably originated by deformation in close connection with the magmatism at 1,470–1,450 Ma. Most titanite U–Pb ages fall between 1,450 and 1,430 Ma, reflecting post-magmatic or post-metamorphic cooling. Granitoid magmatism at ca. 1.45 Ga along the southwestern margin of the East European Craton has previously been reported from southern Sweden and Lithuania. The ages obtained in this study indicate that the Bornholm magmatism also was part of this Mesoproterozoic event.     

A lead isotopic study of the Stillwater Complex,Montana: constraints on crustal contamination and source regions

Analyses of the Pb isotopic compositions of plagioclase from 23 samples covering the stratigraphic thickness of the Stillwater Complex indicate a narrow range of apparent initial isotopic compositions (²⁰⁶Pb/ ²⁰⁴Pb=13.95; ²⁰⁷Pb/²⁰⁴Pb=14.95–15.01; ²⁰⁸Pb/²⁰⁴Pb=33.6). The uniformity of our data is in contrast to, but not necessarily contradictory to, other recent investigations which give indications that the complex formed by repeated injection of magmas with at least two distinct compositions that were presumably derived from different source regions. Samples from the Basal series of the complex have consistently higher ²⁰⁷Pb/²⁰⁴Pb ratios, suggesting either minor contamination from adjacent country rocks or a slight distinction between parental magmas. Apparent initial Pb isotopic compositions of the complex are very radiogenic compared to Late Archean model-mantle values, but are nearly identical to initial Pb isotopic compositions found for the the adjacent, slightly older (2.73–2.79 Ga), Late Archean crustal suite in the Beartooth Mountains. Contamination of magmas parental to the Stillwater Complex by the Late Archean crustal suite is rejected for two reasons: (1) Th and U concentrations in Stillwater rocks and plagioclase are very low (about 0.08 and 0.02 ppm respectively), yet Th/U ratios are uniform at about 4, in contrast to the highly variable (2–26) but often high Th/U ratios found for the Late Archean crustal complex; (2) it seems improbable that any contamination process would have adjusted the isotopic compositions of the diverse magmas entering the Stillwater chamber to near-identical values. The preferred hypothesis to explain the Pb isotopic data for the Stillwater Complex and the associated Late Archean crustal suite involves a major Late Archean crust-forming event that resulted in a compositionally complex crust/mantle system with relatively homogeneous and unusual Pb isotopic compositions. The parental magmas of the Stillwater Complex were generated at different levels within this crust/mantle system, before isotopic contrasts could develop by radioactive decay within compositionally discrete reservoirs. This situation limits the utility of all isotopic tracer systems in discriminating among the various mantle and crustal reservoirs that may have affected the final isotopic character of the Stillwater magmas. The late Archean crustal complex and the Stillwater Complex melts were ultimately derived from the same distinct mantle without obvious direct interaction with the Middle to Early Archean crust present in the region.     

Rb-Sr and U-Pb systematics of metasedimentary carbonate rocks: The Paleoproterozoic Kuetsjarvi Formation of the Pechenga Greenstone Belt, Kola Peninsula

The Rb-Sr and U-Pb systematics have been studied in the metasedimentary carbonate rocks from the Paleoproterozoic Kuetsjarvi Formation. Samples were taken from the borehole drilled in the northern zone of the Pechenga Greenstone Belt in the northwestern Kola Peninsula. The carbonate section of the formation is made up of three units (from the bottom to top): (I) dolomite (68 m), (II) calcareous-dolomite (9 m), and (III) clayey calcareous (1 m) ones. Dolomites (Mg/Ca = 0.55–0.61) from the lowermost unit I contain 70.3–111 ppm Sr. Initial ⁸⁷Sr/⁸⁶Sr ratio in them varies within 0.70560–0.70623 and characterizes the primary continental-lacustrine carbonate sediments. Calcareous dolomites (Mg/Ca = 0.39–0.59) and dolomitic limestones of units II and III (Mg/Ca = 0.02–0.36) are enriched in Sr (285–745 and 550–1750 ppm, respectively). Initial ⁸⁷Sr/⁸⁶Sr ratios in these rocks (0.70406–0.70486 and 0.70407–0.70431, respectively) fall within the range typical of the Jatulian seawater, which indicates that the carbonate sediments of two upper units were formed in an open marine basin. Study of dolomites from unit I showed that the Svecofennian metamorphism more significantly affected the U-Pb systems of carbonate rocks as compared to their Rb-Sr systems. In the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram, most data points corresponding to the carbonate constituent of dolomites define isochron with an age of 1900 ± 25 Ma (MSWD = 0.5). The same samples define a positive correlation in the ²⁰⁸Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb plot. Since sedimentary carbonates usually do not contain Th, this correlation points to secondary enrichment of the studied dolomites in Th or thorogenic ²⁰⁸Pb. Hence, the obtained Pb-Pb dating can be regarded as the age of the Svecofennian metamorphic event. Three samples from dolomites of unit I lack any disturbance of the initial U-Th-Pb systematics, but their trend in the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram deviates from the 1900 Ma isochron. Based on these samples, the model U-Pb premetamorphic age of the Kuetsjarvi carbonate sediments is 2075–2100 Ma. This interval is consistent with the age range of the Lomagundi-Jatulian event, which was responsible for the formation of carbonate sediments with high positive δ¹³C values.     

Inclusion-localised crystal-plasticity,dynamic porosity,and fast-diffusion pathway generation in zircon

A population of oscillatory zoned, igneous zircon grains in a Javanese andesite contains fluid and mineral inclusions (up to 10 μm across) trapped during zircon growth. Orientation contrast imaging and orientation mapping by electron backscatter diffraction reveal that crystal-plastic deformation overprints growth zoning and has localized around 1–10 μm pores and inclusions. Cumulative crystallographic misorientation of up to 25° around pores and inclusions in zircon is predominantly accommodated by low-angle (<5°) orientation boundaries, with few free dislocations in subgrain interiors. Low-angle boundaries are curved, with multiple orientation segments at the sub-micrometer scale. Misorientation axes associated with the most common boundaries align with the zircon c-axis and are consistent with dislocation creep dominated by <100>(010) slip. A distinctly different population of sub-micron pores is present along subgrain boundaries and their triple junctions. These are interpreted to have formed as a geometric consequence of dislocation interaction during crystal-plasticity. Dislocation creep microstructures are spatially related to differences in cathodoluminescence spectra that indicate variations in the abundance of CL-active rare earth elements. The extent of the modification suggests deformation-related fast-pathway diffusion distances that are over five orders of magnitude greater than expected for volume diffusion. This enhanced diffusion is interpreted to represent a combination of fast-diffusion pathways associated with creep cavitation, dislocations and along low-angle boundaries. These new data indicate that ductile deformation localised around inclusions can provide fast pathways for geochemical exchange. These pathways may provide links to the zircon grain boundary, thus negating the widely held assumption that inclusions in fracture-free zircon are geochemically armoured once they are physically enclosed.     

Ore geochemistry,zircon mineralogy,and genesis of the Sakharjok Y-Zr deposit,Kola Peninsula,Russia

The Sakharjok Y-Zr deposit in Kola Peninsula is related to the fissure alkaline intrusion of the same name. The intrusion ∼7 km in extent and 4–5 km² in area of its exposed part is composed of Neoarchean (2.68–2.61 Ma) alkali and nepheline syenites, which cut through the Archean alkali granite and gneissic granodiorite. Mineralization is localized in the nepheline syenite body as linear zones 200–1350 m in extent and 3–30 m in thickness, which strike conformably to primary magmatic banding and trachytoid texture of nepheline syenite. The ore is similar to the host rocks in petrography and chemistry and only differs from them in enrichment in zircon, britholite-(Y), and pyrochlore. Judging from geochemical attributes (high HSFE and some incompatible element contents (1000–5000 ppm Zr, 200–600 ppm Nb, 100–500 ppm Y, 0.1–0.3 wt % REE, 400–900 ppm Rb), REE pattern, Th/U, Y/Nb, and Yb/Ta ratios), nepheline syenite was derived from an enriched mantle source similar to that of contemporary OIB and was formed as an evolved product of long-term fractional crystallization of primary alkali basaltic melt. The ore concentrations are caused by unique composition of nepheline syenite magma (high Zr, Y, REE, Nb contents), which underwent subsequent intrachamber fractionation. Mineralogical features of zircon-the main ore mineral—demonstrate its long multistage crystallization. The inner zones of prismatic crystals with high ZrO₂/HfO₂ ratio (90, on average) grew during early magmatic stage at a temperature of 900–850°C. The inner zones of dipyramidal crystals with average ZrO₂/HfO₂ = 63 formed during late magmatic stage at a temperature of ∼500°C. The zircon pertaining to the postmagmatic hydrothermal stage is distinguished by the lowest ZrO₂/HfO₂ ratio (29, on average), porous fabric, abundant inclusions, and crystallization temperature below 500°C. The progressive decrease in ZrO₂/HfO₂ ratio was caused by evolution of melt and postmagmatic solution. The metamorphic zircon rims relics of earlier crystals and occurs as individual rhythmically zoned grains with an averaged ZrO₂/HfO₂ ratio (45, on average) similar to that of the bulk ore composition. The metamorphic zircon is depleted in uranium in comparison with magmatic zircon, owing to selective removal of U by aqueous metamorphic solutions. Zircon from the Sakharjok deposit is characterized by low concentrations of detrimental impurities, in particular, contains only 10–90 ppm U and 10–80 ppm Th, and thus can be used in various fields of application.     

A Potential (U‐Th)/He Zircon Reference Material from Penglai Zircon Megacrysts

In this study (U‐Th)/He dating of the Penglai zircons, which occur as abundant megacrysts in Neogene alkaline basalts in northern Hainan Province, south‐eastern China, was undertaken. A weighted mean age of 4.06 ± 0.35 Ma (2s) with a mean square weighted deviation (MSWD) of 1.79 was obtained from eighteen fragments of four zircon megacrysts using single‐crystal laser fusion He determinations and the U‐Th isotope dilution (ID) method. The (U‐Th)/He ages are consistent, homogeneous and systematically slightly younger than the preferred ²⁰⁶Pb/²³⁸U age of 4.4 ± 0.1 Ma (95% confidence interval) determined by ID‐TIMS and subsequently published U‐Pb results. The U‐Pb isotopic system in zircon has a high closure temperature of ~ 900 °C, and the preferred U‐Pb age may record both the time since eruption and the zircon residence time in the magma chamber. In contrast, the closure temperature of the zircon (U‐Th)/He system is ~ 190 °C and the zircon megacrysts were brought quickly to the surface by the host basaltic magma. Thus, the (U‐Th)/He age represents the timing of the eruption. Based on the unlimited quantity, large grain size, mostly weak broad zoning, rapid cooling and homogenous (U‐Th)/He ages, we consider the Penglai zircons suitable for use as a reference material in (U‐Th)/He isotope geochronology.     

内蒙古道伦达坝铜钨锡矿床LA-ICP-MS锆石和锡石U-Pb年龄及其地质意义

道伦达坝矿床位于大兴安岭南段,是一个铜钨锡矿床,其铜、钨、锡储量均达中型。矿体呈脉状,主要产于二叠系砂板岩中的断裂破碎带中,华力西期黑云母花岗岩中的断裂破碎带中亦赋存有矿体。文章选取2件石英-萤石-白云母-电气石-锡石-黑钨矿阶段的矿石样品对其中的进行了LA-ICP-MS U-Pb定年,获得2件样品的~(207)Pb/~(206)Pb-~(238)U/~(206)Pb谐和年龄分别为(134.7±6.6)Ma(MSWD=1.4)和(136.8±7.4)Ma(MSWD=1.7),~(206)Pb/~(207)Pb-~(238)U/~(207)Pb等时线年龄分别为(132±12)Ma(MSWD=0.76)和(135±13)Ma(MSWD=0.9)。锡石定年结果表明,道伦达坝矿床形成于早白垩世。对矿区外围张家营子岩体中的斑状细粒花岗岩进行了LA-ICP-MS锆石U-Pb测年,获得的~(206)Pb/~(238)U加权平均年龄为(135±1)Ma(MSWD=1.3),该岩体的形成年龄与道伦达坝矿床的成矿年龄在误差范围内一致。本次定年结果表明道伦达坝矿床形成于早白垩世,与同期的花岗质岩浆活动有密切的成因联系,该矿床属于与花岗岩有关的岩浆热液脉型矿床。     

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.     

Lattice distortion in a zircon population and its effects on trace element mobility and U–Th–Pb isotope systematics: examples from the Lewisian Gneiss Complex, northwest Scotland

Zircon is a key mineral in geochemical and geochronological studies in a range of geological settings as it is mechanically and chemically robust. However, distortion of its crystal lattice can facilitate enhanced diffusion of key elements such as U and Pb. Electron backscatter diffraction (EBSD) analysis of ninety-nine zircons from the Lewisian Gneiss Complex (LGC) of northwest Scotland has revealed five zircons with lattice distortion. The distortion can take the form of gradual bending of the lattice or division of the crystal into subgrains. Zircon lattices are distorted because of either post-crystallisation plastic distortion or growth defects. Three of the five distorted zircons, along with many of the undistorted zircons in the population, were analysed by ion microprobe to measure U and Pb isotopes, Ti and REEs. Comparison of Th/U ratio, ²⁰⁷Pb/²⁰⁶Pb age, REE profile and Ti concentration between zircons with and without lattice distortion suggests that the distortion is variably affecting the concentration of these trace elements and isotopes within single crystals, within samples and between localities. REE patterns vary heterogeneously, sometimes relatively depleted in heavy REEs or lacking a Eu anomaly. Ti-in-zircon thermometry records temperatures that were either low (~700 °C) or high (>900 °C) relative to undistorted zircons. One distorted zircon records apparent ²⁰⁷Pb/²⁰⁶Pb isotopic ages (?3.0 to +0.3 % discordance) in the range of ~2,420–2,450 Ma but this does not correlate with any previously dated tectonothermal event in the LGC. Two other distorted zircons give discordant ages of 2,331 ± 22 and 2,266 ± 40 Ma, defining a discordia lower intercept within error of a late amphibolite-facies tectonothermal event. This illustrates that Pb may be mobilised in distorted zircons at lower metamorphic grade than in undistorted zircons. These differences in trace element abundances and isotope systematics in distorted zircons relative to undistorted zircons are generally interpreted to have been facilitated by subgrain walls. Trace elements and isotopes would have moved from undistorted lattice into these subgrain walls as their chemical potential is modified due to the presence of the dislocations which make up the subgrain wall. Subgrain walls provided pathways for chemical exchange between crystal and surroundings. Only five per cent of zircons in this population have lattice distortion suggesting it will not have a major impact on zircon geochronology studies, particularly as three of the five distorted zircons are from strongly deformed rocks not normally sampled in such studies. However, this does suggest there may be a case for EBSD analysis of zircons prior to geochemical analysis when zircons from highly deformed rocks are to be investigated.     

Refining the timing of eclogite metamorphism: a geochemical,petrological, Sm-Nd and U-Pb case study from the Pohorje Mountains,Slovenia (Eastern Alps)

High-pressure metamorphism in the Pohorje Mountains of Slovenia (Austroalpine unit, Eastern Alps) affected N-MORB type metabasic and metapelitic lithologies. Thermodynamic calculations and equilibrium phase diagrams of kyanite–phengite-bearing eclogites reveal PT conditions of >2.1 GPa at T<750°C, but within the stability field of quartz. Metapelitic eclogite country rocks contain the assemblage garnet + phengite + kyanite + quartz, for which calculated peak pressure conditions are in good agreement with results obtained from eclogite samples. The eclogites contain a single population of spherical zircon with a low Th/U ratio. Combined constraints on the age of metamorphism come from U/Pb zircon as well as garnet–whole rock and mineral–mineral Sm-Nd analyses from eclogites. A coherent cluster of single zircon analyses yields a ²⁰⁶Pb/²³⁸U age of 90.7±1.0 Ma that is in good agreement with results from Sm-Nd garnet–whole rock regression of 90.7±3.9 and 90.1±2.0 Ma (εNd: +8) for two eclogite samples. The agreement between U-Pb and Sm-Nd age data strongly suggests an age of approximately 90 Ma for the pressure peak of the eclogites in the Pohorje Mountains. The presence of garnet, omphacite and quartz inclusions in unfractured zircon indicates high-pressure rather than ultrahigh pressure conditions. The analysed metapelite sample yields a Sm-Nd garnet–whole rock scatterchron age of 97±15 Ma. These data probably support a single P-T loop for mafic and pelitic lithologies of the Pohorje area and a late Cretaceous high-pressure event that affected the entire easternmost Austroalpine basement including the Koralpe and Saualpe eclogite type locality in the course of the complex collision of the Apulian microplate and Europe.     

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.     

内蒙古大青山地区英安岩LA-ICP-MS锆石U-Pb年龄及其构造意义

在内蒙古大青山地区逆冲推覆构造所截切的英安岩中获得锆石~(207)Pb/~(206)Pb表面年龄加权平均值为1870±19Ma,认为英安岩为华北克拉通古元古代末—新元古代一次裂解事件的产物.同时,据安山岩锆石U-Pb年龄谐和度(102)较好的锆石~(206)Pb/~(238)U表面年龄436±4Ma及英安岩锆石U-Pb年龄谐和度(104)较好的锆石~(206)Pb/~(238)U表面年龄153±2Ma和160±2Ma,表明大青山地区逆冲推覆构造存在构造复活或构造追踪现象。这一认识为大青山地区逆冲推覆构造的研究积累了新的资料,提供了新的研究思路。     

Precise geochronology of phoscorites and carbonatites:: The critical role of U-series disequilibrium in age interpretations

We present the results of a comparative study of several geochronometer minerals (baddeleyite, zircon, apatite, phlogopite and tetraferriphlogopite) and isotopic systems (U-Pb, Th-Pb and Rb-Sr) from phoscorites (magnetite-forsterite-apatite-calcite rocks) and carbonatites of the Kovdor ultramafic-alkaline-carbonatite massif, Kola Peninsula, Russia. Uranium, thorium and their decay products are extremely fractionated by minerals that crystallise from carbonatite and phoscorite magma. We obtain high-precision ages from different chronometers, compare their accuracy, and evaluate the role of geochronological pitfalls of initial radioactive disequilibrium, differential migration of radiogenic isotopes, and inaccurate decay constants.Apatite yielded concordant U-Th-Pb ages between 376 and 380 Ma. The accuracy of the apatite ²³⁸U-²⁰⁶Pb ages is, however, compromised by uncertainty in the amount of radiogenic ²⁰⁶Pb produced from initial excess ²³⁰Th. The ²³⁵U-²⁰⁷Pb ages are relatively imprecise due to large common Pb correction and the uncertainty in the initial Pb isotopic composition. The Th-Pb system yields a more precise age of 376.4 ± 0.6 Ma.Zircon from two carbonatite samples is characterised by moderate to low U contents, high Th contents, and very high Th/U ratios up to 9000. The ²⁰⁶Pb*/²³⁸U systems in the zircon are strongly affected by the presence of excess ²⁰⁶Pb*, produced by decay of initial ²³⁰Th. The ²⁰⁸Pb*/²³²Th ages of zircon from both carbonatite samples are uniform and yield a weighted average of 377.52 ± 0.94 Ma.Baddeleyite U-Pb analyses are 3 to 6% normally discordant and have variable ²⁰⁷Pb*/²⁰⁶Pb* apparent ages. Eleven alteration-free baddeleyite fractions from three samples with no evidence for Pb loss yield uniform ²⁰⁶Pb*/²³⁸U ages with a weighted average of 378.54±0.23 Ma (378.64 Ma after correction for initial ²³⁰Th deficiency), which we consider the best estimate for age of the phoscorite-carbonatite body of the Kovdor massif. The ²⁰⁶Pb*/²³⁸U ages of baddeleyite fractions from five other samples spread between 378.5 and 373 Ma, indicating a variable lead loss up to 1.5%. The anomalously old ²⁰⁷Pb/²³⁵U and ²⁰⁷Pb/²⁰⁶Pb ages are consistent with the presence of excess radiogenic ²⁰⁷Pb* in the baddeleyite. We interpret this as a result of preferential partitioning of ²³¹Pa to baddeleyite.Fifteen phlogopite and tetraferriphlogopite fractions from five carbonatite and phoscorite samples yielded precise Rb-Sr isochron age of 372.2 ± 1.5 Ma, which is 5 to 7 m.y. younger than our best estimate based on U-Th-Pb age values. This difference is unlikely to be a result of the disturbance or late closure of Rb-Sr system in phlogopite, but rather suggests that the accepted decay constant of ⁸⁷Rb is too high.Comparative study of multiple geochronometer minerals from the Kovdor massif has revealed an exceptional complexity of isotopic systems. Reliable ages can be understood through systematic analysis of possible sources of distortion. No single geochronometer is sufficiently reliable in these rocks. Th-Pb and Rb-Sr can be a very useful supplement to U-Pb geochronometry, but the routine use of these geochronometers together will require more precise and accurate determination of decay constants for ²³²Th and ⁸⁷Rb.     

Devonian to Carboniferous collision in the Greenland Caledonides: U-Pb zircon and Sm-Nd ages of high-pressure and ultrahigh-pressure metamorphism

A variety of eclogites from an east-west transect across the North-East Greenland eclogite province have been studied to establish the timing of high pressure (HP) and ultrahigh-pressure (UHP) metamorphism in this northern segment of the Laurentian margin. Garnet + omphacite ± amphibole + whole rock Sm-Nd isochrons from a quartz eclogite, a garnet + omphacite + rutile eclogite and a partially melted zoisite eclogite in the western HP belt are 401±2, 402±9 and 414±18 Ma, respectively. Corresponding sensitive high-resolution ion microprobe (SHRIMP) ²⁰⁶Pb/²³⁸U ages of metamorphic zircon in the same samples are 401±7, 414±13, and 393 ±10 Ma. Metamorphic zircon domains were identified using morphology, cathodoluminescence (CL) imaging, U, Th, Th/U and trace element contents. Zircon from the quartz eclogite and the garnet + omphacite + rutile eclogite are typical of eclogite facies zircon with rounded to subhedral shapes, patchy to homogenous CL domains, low U, and very low Th and Th/U. The partially melted eclogite contains euhedral zircons with dark, sector-zoned, higher U, Th and Th/U inherited cores. Three cores give a Paleoproterozoic ²⁰⁷Pb/²⁰⁶Pb age of 1,962±27 Ma, interpreted as the age of the leucogabbroic protolith. CL images of the bright overgrowths show faint oscillatory zoning next to homogenous areas that indicate zircon growth in the presence of a HP melt and later recrystallization. Additional evidence that zircon grew during eclogite facies conditions is the lack of a Eu anomaly in the trace element data for all the samples. These results, combined with additional less precise Sm-Nd ages and our earlier work, point to a Devonian age of HP metamorphism in the western and central portions of the eclogite province. An UHP kyanite eclogite from the eastern part of the transect contains equant metamorphic zircon with homogeneous to patchy zoning in CL and HP inclusions of garnet, omphacite and kyanite. These zircons have slightly higher U, Th and Th/U values than the HP ones, no Eu anomaly, and are thus comparable to UHP zircons in the literature. The ²⁰⁶Pb/²³⁸U age of these zircons is 360±5 Ma, much younger than the HP eclogites. The same sample gives a Sm-Nd age of 342±6 Ma. Unlike the HP eclogites, the Sm-Nd age of the UHP rock is ca. 20 Ma younger than the U-Pb zircon age and most likely records slow cooling through the closure temperature, since peak temperatures were in excess of 900°C. Widespread HP metamorphism of both the Laurentian and Baltica continental margins marks the culmination of this continent–continent collision in the Devonian. Carboniferous UHP conditions, though localized in the east, suggest a prolonged collisional history rather than a short-lived Scandian orogeny. The traditional Silurian Scandian orogeny should thus be extended through the Devonian.     

Simultaneous horst-basin formation and magmatism during Late Variscan transtension: evidence from 40Ar/39Ar and 207Pb/206Pb geochronology in the Ruhla Crystalline Complex

40 Ar/³⁹Ar–mica and ²⁰⁷Pb/²⁰⁶Pb–zircon dates are presented and combined with existing P–T data and the sedimentary record. These data indicate that the RCC was faulted into three segments which underwent different exhumation histories during the Late Carboniferous/Early Permian. The eastern segment shows ⁴⁰Ar/³⁹Ar–biotite data of336 ±4 and 323±3 Ma. Furthermore, it is intruded by the Thuringian Hauptgranite dated at 337±4 Ma by the ²⁰⁷Pb/²⁰⁶Pb single zircon method. At approximately 300 Ma rocks of the eastern segment were finally exposed and, subsequently, subsided as part of the Oberhof pull-apart basin, filled by Late Carboniferous/Early Permian molasse sediments and volcanic rocks (296–285 Ma; Goll 1996). A similar Late Carboniferous evolution is inferred for the western segment, since it is also overlain by Upper Carboniferous volcanic rocks. In contrast to the eastern and western segments, distinctly younger intrusion and cooling ages were recorded for the central segment of the RCC (⁴⁰Ar/³⁹Ar muscovite: 311±3 Ma; ⁴⁰Ar/³⁹Ar biotite: 293–288±3 Ma) that was intruded by the Trusetal Granite, the Ruhla Granite and Brotterode Diorite (²⁰⁷Pb/²⁰⁶Pb single zircon: 298±2, 295±3, 289±4 Ma, respectively). These young data are unique in the MGCR and testify that plutonic activity and cooling of basement rocks took place simultaneously with basin formation and volcanism in the eastern and western segments. Overlying Upper Permian (Zechstein) and Triassic sediments indicate final exposure of the central segment by approximately 260 Ma, as a part of the Ruhla-Schleusingen Horst. Combination of these results with P–T data from the contact aureole of the Trusetal granite indicate that the central segment was unroofed by at least 8.5 km during the Late Carboniferous. The Late Carboniferous/Early Permian horst-basin formation, documented in the RCC, is due to dextral transtensional movements along the NW-trending Franconian fault system. It may have been enhanced by mantle upwelling widespread in Central Europe during the Early Permian that also caused intensive magmatism in the Thuringian Forest region. Received: 2 February 1999 / Accepted: 15 November 1999