Determination of Sm‐Nd Isotopic Compositions in Fifteen Geological Materials Using Laser Ablation MC‐ICP‐MS and Application to Monazite Geochronology of Metasedimentary Rock in the North China Craton

In this study, we report both ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd values in twelve minerals (apatite, titanite, monazite and eudialyte) based on analyses over 4 years using LA‐MC‐ICP‐MS. The positive correlation between the measured β_Sm and β_Nd (r² = 0.9981) over this time in our laboratory demonstrates the excellent long‐term stability of the method. Compared with the normal method, Sm and Nd signal intensities were improved by a factor of 2.9 with the use of X skimmer and Jet sample cones in combination with the addition of nitrogen at 3–6 ml min^?1 to the central gas flow. The enhancement of signal intensity benefits the accurate in situ determination of the Sm‐Nd isotopes of samples poor in these elements. ¹⁴³Nd/¹⁴⁴Nd values were also determined in two manganese nodules and GSMC Co‐rich crust with low mass fractions of Nd (94–293 μg g^?1). Generally, most of the obtained Sm‐Nd isotopic compositions in these geological materials are consistent with published values. ‘External reproducibility’ (2s) of ¹⁴³Nd/¹⁴⁴Nd and ¹⁴⁷Sm/¹⁴⁴Nd was typically better than 0.06‰ and 2.5‰, respectively, demonstrating that the Durango, Otter Lake, NW‐1 and MAD apatites, the Khan, and OLT‐1 titanites, MGMH#117531 monazite and LV01 eudialyte are promising candidate reference materials for in situ Sm‐Nd isotopic determinations. The Trebilcock, Mae Klang and 44069 monazites are only suitable for in situ Nd isotopic determinations because of their heterogeneous Sm/Nd compositions. The heterogeneous Sm‐Nd composition of titanite BLR‐1 demonstrates that it is not a suitable reference material for in situ Sm‐Nd isotopic determinations. Deep‐sea samples (NOD‐A‐1 and NOD‐P‐1 manganese nodule, GSMC Co‐rich crust) with low mass fractions of Nd also show homogenous Nd isotopic compositions. Sm‐Nd isotopic ratios of a monazite (MQG‐22) from the North China Craton were measured as a case study and gave a ¹⁴⁷Sm‐¹⁴³Nd isochron age of 1792 ± 35 Ma (MSWD = 3.2) consistent with the published metamorphic age of the host metasedimentary rocks. The results for both candidate reference materials and geological samples demonstrate that the in situ LA‐MC‐ICP‐MS analytical protocol described is feasible and robust for research in geological evolution.     

In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

Integrated garnet and zircon–titanite geochronology constrains the evolution of ultra‐high–pressure terranes: An example from the Sulu orogen

Dating ultra‐high–pressure (UHP) metamorphic rocks provides important timing constraints on deep subduction zone processes. Eclogites, deeply subducted rocks now exposed at the surface, undergo a wide range of metamorphic conditions (i.e. deep subduction and exhumation) and their mineralogy can preserve a detailed record of chronologic information of these dynamic processes. Here, we present an approach that integrates multiple radiogenic isotope systems in the same sample to provide a more complete timeline for the subduction–collision–exhumation processes, based on eclogites from the Dabie–Sulu orogenic belt in eastern China, one of the largest UHP terranes on Earth. In this study, we integrate garnet Lu–Hf and Sm–Nd ages with zircon and titanite U–Pb ages for three eclogite samples from the Sulu UHP terrane. We combine this age information with Zr‐in‐rutile temperature estimates, and relate these multiple chronometers to different P–T conditions. Two types of rutile, one present as inclusions in garnet and the other in the matrix, record the temperatures of UHP conditions and a hotter stage, subsequent to the peak pressure (‘hot exhumation') respectively. Garnet Lu–Hf ages (c. 238–235 Ma) record the initial prograde growth of garnet, while coupled Sm–Nd ages (c. 219–213 Ma) reflect cooling following hot exhumation. The maximum duration of UHP conditions is constrained by the age difference of these two systems in garnet (c. 235–220 Ma). Complementary zircon and titanite U–Pb ages of c. 235–230 Ma and c. 216–206 Ma provide further constraints on the timing of prograde metamorphism and the ‘cold exhumation' respectively. We demonstrate that timing of various metamorphic stages can thus be determined by employing complementary chronometers from the same samples. These age results, combined with published data from adjacent areas, show lateral diachroneity in the Dabie–Sulu orogeny. Three sub‐blocks are thus defined by progressively younger garnet ages: western Dabie (243–238 Ma), eastern Dabie–northern Sulu (238–235 Ma) and southern Sulu terranes (225–220 Ma), which possibly correlate to different crustal slices in the recently proposed subduction channel model. These observed lateral chronologic variations in a large UHP terrane can possibly be extended to other suture zones.     

High‐Precision Sr‐Nd‐Hf‐Pb Isotopic Composition of Chinese Geological Standard Glass Reference Materials CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 by MC‐ICP‐MS and TIMS

To assess the homogeneity of and provide the first Sr‐Nd‐Hf‐Pb isotopic reference values for the Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5, we measured these isotopes in several measurement sessions over the course of nearly 3 years. The results were obtained by high‐precision MC‐ICP‐MS and TIMS. Our investigation indicates that these CGSG glass reference materials are homogenous with regard to Sr‐Nd‐Hf‐Pb isotopic distribution and are therefore suitable geochemical materials for Sr‐Nd‐Hf‐Pb isotope measurements. Clear differences in Sr‐Nd‐Hf‐Pb isotopic composition were observed between the glasses and the original powdered rock reference materials (CGSG‐2 and GSR‐7, and especially CGSG‐5 and GSR‐2) because of flux addition during preparation of the glasses. The new Sr‐Nd‐Hf‐Pb isotope data provided here might be useful to the geochemical community for in situ and bulk analysis.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).     

The Diamantina Monazite: A New Low‐Th Reference Material for Microanalysis

Most monazite reference materials (RMs) for in situ U‐Pb geochronology are rich in Th; however, many hydrothermal ore deposits contain monazite that is low in trace element contents, including Th, U and Pb. Because of potential problems with matrix effects and the lack of appropriate matrix‐matched RMs, such variations can bias dating of hydrothermal deposits. In this paper, we describe a polycrystalline low‐U and low‐Th Diamantina monazite from the Espinhaço Range, SE Brazil. It has a U‐Pb ID‐TIMS weighted mean ²⁰⁷Pb^*/²³⁵U ratio of 0.62913 ± 0.00079, ²⁰⁶Pb^*/²³⁸U of 0.079861 ± 0.000088 and ²⁰⁷Pb^*/²⁰⁶Pb^* of 0.057130 ± 0.000031, yielding a weighted mean ²⁰⁶Pb^*/²³⁸U date of 495.26 ± 0.54 Ma (95% c.l.). In situ dates acquired with different methods (LA‐(Q, SF, MC)‐ICP‐MS and SIMS) are within uncertainty of the ID‐TIMS data. U‐Pb LA‐(Q, MC)‐ICP‐MS runs, using Diamantina as a primary RM, reproduced the ages of other established RMs within < 1% deviation. The LA‐MC‐ICP‐MS analyses yielded homogeneous Sm‐Nd isotopic compositions (¹⁴³Nd/¹⁴⁴Nd = 0.511427 ± 23, 2s; ¹⁴⁷Sm/¹⁴⁴Nd = 0.1177 ± 13, 2s) and εNd_(495 Ma) of ?18.7 ± 0.5 (2s). SIMS oxygen isotope determinations showed measurement reproducibility better than ± 0.3‰ (2s), confirming Diamantina's relative homogeneity at test portion masses below 1 ng.     

Crustal response to continental collisions between the Tibet, Indian, South China and North China Blocks: geochronological constraints from the Songpan-Garzê Orogenic Belt, western China

We report SHRIMP U–Th–Pb monazite, conventional U–Pb titanite, Sm–Nd garnet and Rb–Sr muscovite and biotite ages for metamorphic rocks from the Danba Domal Metamorphic Terrane in the eastern Songpan‐Garzê Orogenic Belt (eastern Tibet Plateau). These ages are used to determine the timing of polyphase metamorphic events and the subsequent cooling history. The oldest U–Th–Pb monazite and Sm–Nd garnet ages constrain an early Barrovian metamorphism (M1) in the interval c. 204–190 Ma, coincident with extensive Indosinian granitic magmatism throughout the Songpan‐Garzê Orogenic Belt. A second, higher‐grade sillimanite‐grade metamorphic event (M2), recorded only in the northern part of the Danba terrane, was dated at c. 168–158 Ma by a combination of U–Th–Pb monazite and titanite and Sm–Nd garnet ages. It is suggested that M1 was a thermal event that affected the entire orogenic belt while M2 may represent a local thermal perturbation. Rb–Sr muscovite ages range from c. 138–100 Ma, whereas Rb–Sr biotite ages cluster at c. 34–24 Ma. These ages document regional cooling at rates of c. 2–3 °C Myr^?1 following the M1 peak for most of the terrane. However, those parts of the terrane affected by the higher‐temperature M2 event (e.g. the migmatite zone) experienced initially more rapid (c. 8 °C Myr^?1) cooling after peak M2 before joining the regional slow cooling path defined by the rest of the terrane at c. 138 Ma. Regional slow cooling between c. 138 and c. 30 Ma is thought to be the result of post‐tectonic isostatic uplift after extensive crustal thickening caused by collision of the South and North China Blocks. The clustering of biotite Rb–Sr ages marks the onset of rapid uplift across the entire terrane commencing at c. 30–20 Ma. This cooling history is shared with many other regions of the Tibet Plateau, suggesting that uplift of the Tibet Plateau (including the Songpan‐Garzê Orogenic Belt) occurred predominantly in the last c. 30 Myr as a response to the continuing northwards collision of India with Eurasia.     

RMJG Rutile: A New Natural Reference Material for Microbeam U‐Pb Dating and Hf Isotopic Analysis

Matrix‐matched reference materials are necessary for accurate microbeam U‐Pb dating and Hf isotopic determination. This study introduces the RMJG rutile as a new potential reference material, which was separated from Palaeoproterozoic pelitic granulites collected in Hebei Province, China. LA‐ICP‐MS measurements indicate the RMJG rutile has extremely low Th (< 0.003 ± 0.01 µg g^?1) and common Pb contents, but high Hf (102 ± 34 µg g^?1), U (61 ± 11 µg g^?1), and radiogenic Pb (~ 20 µg g^?1) contents. Moreover, the rutile yields relatively constant U‐Pb ages and Hf isotopic data. The LA‐ICP‐MS analyses suggest that this rutile has a concordant U‐Pb age with a statistical mean ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages of 1749.9 ± 32.1 Ma and 1750.0 ± 26.4 Ma, respectively (2s), which are statistically indistinguishable from its ID‐TIMS ages (1750.6 ± 8.4 and 1750.1 ± 4.7 Ma). Precise determination of the ¹⁷⁶Hf/¹⁷⁷Hf ratio by MC‐ICP‐MS in solution mode (0.281652 ± 0.000006) is in good agreement with the statistical mean of the LA‐MC‐ICP‐MS measurements (0.28166 ± 0.00018). Therefore, the limited variations of RMJG U‐Pb age and Hf isotopic composition together with its extremely low common Pb and high Hf, U and Pb contents make it an ideal calibration and monitor reference material for LA‐ICP‐MS measurements.     

U‐Pb Geochronological and Thermochronological Time–Temperature Constraints of 40Ar/39Ar Hornblende Reference Material HB3gr

Hornblende from the Lone Grove Pluton, Llano Uplift, Texas, has served as an irradiation reference material in ⁴⁰Ar/³⁹Ar studies for decades. In order to evaluate the apparent age bias that currently exists between the U‐Pb and ⁴⁰Ar/³⁹Ar systems, zircon and titanite were dated by isotope dilution‐thermal ionisation mass spectrometry (ID‐TIMS) from the same rock from which the hornblende ⁴⁰Ar/³⁹Ar reference material HB3gr is derived. Zircon U‐Pb data indicate initial crystallisation at 1090.10 ± 0.16 Ma (2s), a date that is 1.7% older than the accepted K‐Ar date (1072 ± 14 Ma, 2s) for HB3gr; an offset that exceeds the typical 0.5–1% bias between the two systems, though remaining within uncertainty due to the large uncertainties in the ⁴⁰K decay constant. Zircon data are presented using both EARTHTIME tracers ET535 and ET2535 and are statistically indistinguishable. Single grain titanite analyses range between 1082 ± 0.75 and 1086 ± 0.81 Ma (2s) and are interpreted to record the subsequent cooling following crystallisation at rates between 30 and 50 °C Ma^?1. This is supported by the observation that hornblende ⁴⁰Ar/³⁹Ar dates corrected for decay constant bias are resolvably younger than the zircon U‐Pb date and in good agreement with titanite U‐Pb dates, permitting the conclusion that both titanite U‐Pb and hornblende ⁴⁰Ar/³⁹Ar systems provide a record of cooling.     

A Practical Approach for Collecting Large‐n Detrital Zircon U‐Pb Data sets by Quadrupole LA‐ICP‐MS

A measurement procedure for the rapid acquisition of U‐Pb dates for detrital zircons by quadrupole LA‐ICP‐MS was developed. The procedure achieves a threefold increase in measurement efficiency compared with the most commonly used methods. Utilising reduced background counting times and a shortened ablation period, a throughput of ~ 130 measurements/h can be achieved. The measurement procedure was characterised and validated using data from thirty‐nine sessions acquired over a twelve‐month period. Systematic measurement error in ²⁰⁶Pb/²³⁸U dates for reference materials used for quality control with ages between 28.2 and 2672 Ma was < 1.5%. Average measurement uncertainty, including both random and systematic components, was 1–4% (2s). Interrogation of time‐resolved calculated dates and signal intensities for each measurement allows for the detection and elimination of portions of measurements exhibiting age heterogeneities, zoning, lead loss and contamination by common lead. The measurement procedure diminishes the need to acquire cathodoluminescence imagery for routine detrital zircon applications further increasing throughput and reducing cost. The utility of the measurement procedure is demonstrated by the measurement of samples previously characterised by LA‐MC‐ICP‐MS.     

Rapid U‐Pb Geochronology by Laser Ablation Multi‐Collector ICP‐MS

Detrital zircon (DZ) U‐Pb laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) has revolutionised the way geologists approach many Earth science questions. Although recent research has focused on rapid sample throughput, acquisition rates are limited to 100–300 analyses h^?1. We present a method to acquire zircon U‐Pb dates at rates of 120, 300, 600 and 1200 analyses h^?1 (30, 12, 6 and 3 s per analysis) by multi‐collector LA‐ICP‐MS. We demonstrate the efficacy of this method by analysing twelve zircon reference materials with dates from ~ 3465 to ~ 28 Ma. Mean offset from high‐precision dates increases with faster rates from 0.9% to 1.1%; mean random 1s uncertainty increases from 0.6% to 1.3%. We tested this new method on a sandstone sample previously characterised by large‐n DZ geochronology. Quantitative comparison shows increased correspondence among age distributions comprising > 300 dates. This new method holds promise for DZ geochronology because (a) it requires no major changes to hardware, but rather modifications to software; (b) it yields robust age distributions well‐suited for quantitative analysis and maximum depositional age calculations; (c) there is only a minor sacrifice of accuracy and measurement uncertainty; and (d) there is less burden to researchers in terms of time investment and analytical cost.     

Dating of young (<1 Ma) tephras: Using U‐Pb (zircon) and (U‐Th[‐Sm])/He (zircon,apatite, magnetite) chronometers to unravel the eruption age of a tephra in the Woodlark Rift of Papua New Guinea

The dating of volcanic tephras forms a critical cornerstone of chronostratigraphy and is paramount for the resolution of the geological timescale. (U‐Th[‐Sm])/He dating is an emerging tool in Quaternary tephrochronology and ideally suited to date tephras <1 Ma. We present zircon, magnetite and apatite (U‐Th[‐Sm])/He combined with zircon U‐Pb data for a Pleistocene tephra in syn‐rift strata of the Woodlark Rift in Papua New Guinea. The results reveal a young He age mode (~0.5 to 0.8 Ma), consistent with an autocrystic zircon U‐Pb crystallisation age of 0.8 ± 0.1 Ma, as well as a broad range of older (U‐Th[‐Sm])/He (~1.6 to 10.2 Ma) and U‐Pb (~4.4 to 107 Ma) ages. These data demonstrate the potential of integrated U‐Pb and (U‐Th[‐Sm])/He multi‐method chronometry for dating the youngest coherent age mode, detecting contaminant grains and evaluating the isotopic systematics of these techniques.     

Timing of high-grade metamorphism: Early Palaeozoic U–Pb formation ages of titanite indicate long-standing high-T conditions at the western margin of Gondwana (Argentina, 26–29°S)

Abstract Concordant U–Pb ages of c. 530–510 Ma and c. 470–420 Ma on titanite from calcsilicate, orthogneiss and amphibolite rocks constrain the age of high‐T metamorphism in the Early Palaeozoic mobile belt at the western margin of Proterozoic Gondwana (Argentina, 26–29°S). The U–Pb ages document the time of titanite formation at high‐T conditions according to the stable mineral paragenesis and occurrence of titanite in the metamorphic fabric. The presence of migmatite at all sample sites indicates temperatures were > c. 650 °C. Titanite formed at similar metamorphic conditions at different times on the regional and on the outcrop scale. The titanite crystals preserved their U–Pb isotopic signatures and chemical composition under ongoing upper amphibolite to granulite facies temperatures. Different thermal peaks or deformations are only detected by the different U–Pb ages and not by changes in the mineral paragenesis or metamorphic fabric of the samples. The range of U–Pb ages, e.g. in the Ordovician and Silurian (c. 470, 460, 440, 430, 420 Ma), is interpreted as the effect polyphase deformation with deformation‐enhanced recrystallization of titanite and/or different thermal peaks during a long‐standing, geographically fixed, high‐T regime in the mid‐crust of a continental magmatic arc. A clear correlation of the different ages with distinct tectonic events, e.g. collision of terranes, is not possible based on the present knowledge of the region.     

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.     

High‐pressure metamorphic evolution of eclogite and associated metapelite from the Chuacús complex (Guatemala Suture Zone): Constraints from phase equilibria modelling coupled with Lu‐Hf and U‐Pb geochronology

As is common in suture zones, widespread high‐pressure rocks in the Caribbean region reached eclogite facies conditions close to ultrahigh‐pressure metamorphism. Besides eclogite lenses, abundant metapelitic rocks in the Chuacús complex (Guatemala Suture Zone) also preserve evidence for high‐pressure metamorphism. A comprehensive petrological and geochronological study was undertaken to constrain the tectonometamorphic evolution of eclogite and associated metapelite from this area in central Guatemala. The integration of field and petrological data allows the reconstruction of a previously unknown segment of the prograde P–T path and shows that these contrasting rock types share a common high‐pressure evolution. An early stage of high‐pressure/low‐temperature metamorphism at 18–20 kbar and 530–580°C is indicated by garnet core compositions as well as the nature and composition of mineral inclusions in garnet, including kyanite–jadeite–paragonite in an eclogite, and chloritoid–paragonite–rutile in a pelitic schist. Peak high‐pressure conditions are constrained at 23–25 kbar and 620–690°C by combining mineral assemblages, isopleth thermobarometry and Zr‐in‐rutile thermometry. A garnet/whole‐rock Lu‐Hf date of 101.8 ± 3.1 Ma in the kyanite‐bearing eclogite indicates the timing of final garnet growth at eclogite facies conditions, while a Lu‐Hf date of 95.5 ± 2.1 Ma in the pelitic schist reflects the average age of garnet growth spanning from an early eclogite facies evolution to a final amphibolite facies stage. Concordant U‐Pb LA‐ICP‐MS zircon data from the pelitic schist, in contrast, yield a mean age of 74.0 ± 0.5 Ma, which is equivalent to a U‐Pb monazite lower‐intercept age of 73.6 ± 2.0 Ma in the same sample, and comparable within errors with a less precise U‐Pb lower‐intercept age of 80 ± 13 Ma obtained in post‐eclogitic titanite from the kyanite‐bearing eclogite. These U‐Pb metamorphic ages are interpreted as dating an amphibolite facies overprint. Protolith U‐Pb zircon ages of 167.1 ± 4.2 Ma and 424.6 ± 5.0 Ma from two eclogite samples reveal that mafic precursors in the Chuacús complex originated in multiple tectonotemporal settings from the Silurian to Jurassic. The integration of petrological and geochronological data suggests that subduction of the continental margin of the North American plate (Chuacús complex) beneath the Greater Antilles arc occurred during an Albian‐Cenomanian pre‐collisional stage, and that a subsequent Campanian collisional stage is probably responsible of the amphibolite facies overprint and late syncollisional exhumation.     

MK‐1 Apatite: A New Potential Reference Material for (U‐Th)/He Dating

The (U‐Th)/He dating technique has been widely used for several decades to constrain the timing of low temperature geological processes. Recent research has shown that the commonly used reference material (the Durango apatite) often yields dispersed fragment dates that are beyond analytical uncertainties. Here, we report a new apatite (U‐Th)/He dating reference material, MK‐1, which was collected from the Mogok metamorphic belt in Burma. Electron probe microanalysis and backscattered electron images of two randomly selected fragments indicate that this apatite is chemically and structurally homogeneous. We performed single‐grain (U‐Th)/He dating on thirty randomly selected fragments of this material. (U‐Th)/He dating results from multiple laboratories show that fragments of the MK‐1 apatite megacryst yielded reproducible results, with a mean date of 18.0 ± 0.2 Ma. The Th/U ratio of this apatite is homogeneous. Nine randomly selected fragments registered a narrow range of effective uranium (eU) mass fractions (326–354 μg g^?1), with a mean value of 336.6 ± 10.3 μg g^?1. Twenty‐four in situ (U‐Th)/He dates yielded a mean value of 18.0 ± 0.2 Ma (MSWD = 0.41), indistinguishable from the results obtained by the conventional method. All the results suggest that this apatite has the potential to become a new reference material for (U‐Th)/He geochronology.     

Ultrafast, > 50 Hz LA‐ICP‐MS Spot Analysis Applied to U–Pb Dating of Zircon and other U‐Bearing Minerals

LA‐ICP‐MS U–Pb detrital zircon studies typically analyse 50–200 grains per sample, with the consequent risk that minor but geologically important age components (e.g., the youngest detrital zircon population) are not detected, and higher abundance age components are misrepresented, rendering quantitative comparisons between samples impossible. This study undertook rapid U–Pb LA‐ICP‐MS analyses (8 s per 18–47 μm diameter spot including baseline and ablation) of zircon, apatite, rutile and titanite using an aerosol rapid introduction system (ARIS). As the ARIS resolves individual single pulses at fast sampling rates, spot analyses require a high repetition rate (> 50 Hz) so the signal does not return to baseline and mass sweep times (> 80 ms) that span several laser pulses (i.e., major undersampling of the signal). All rapid U–Pb spot analyses employed 250–300 pulses, repetition rates of 53–65 Hz (total ablation times of 4.1–5.7 s) and low fluence (1.75–2.5 J cm^?2), resulting in pit depths of ca. 15 μm. Zircon, apatite, rutile and titanite reference material data yield an accuracy and precision (2s) of < 1% for pre‐Cenozoic reference materials and < 2% for younger reference materials. We present a detrital zircon data set from a Neoproterozoic tillite where > 1000 grains were analysed in < 3 h with a precision and accuracy comparable to conventional LA‐ICP‐MS analytical protocols, demonstrating the rapid acquisition of huge detrital data sets.     

U‐Th Zircon Dating by Laser Ablation Single Collector Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS)

Zircon crystals in the age range of ca. 10–300 ka can be dated by ²³⁰Th/²³⁸U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr₂O₃⁺) are critical for reliable determination of ²³⁰Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (²³⁰Th)/(²³⁸U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including ²³⁰Th) within the ²³⁸U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on ²³⁰Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).     

Titanite dates crystallization: Slow Pb diffusion during super‐solidus re‐equilibration

Titanite can be found in rocks of wide compositional range, is reactive, growing or regrowing during metamorphic and hydrothermal events, and is generally amenable to U–Pb geochronology. Experimental evidence suggest that titanite has a closure temperature for Pb ranging from 550 to 650°C, and thus titanite dates are commonly interpreted as cooling ages. However, this view has been challenged in recent years by evidence from natural titanite which suggests the closure temperature may be significantly higher (up to 800°C). Here, we investigate titanite in an enclave of migmatitic gneiss included within a granite intrusion. The titanite crystals exhibit textural features characteristic of fluid‐mediated mass transfer processes on length scales of <100 µm. These textural features are associated with variation in both Pb concentrations and distinct U–Pb isotopic compositions. Zr‐in‐titanite thermometry indicates that modification of the titanite occurred at temperatures in excess of 840°C, in the presence of a high‐T silicate melt. The Pb concentration gradients preserved in these titanite crystals are used to determine the diffusivity of Pb in titanite under high‐T conditions. We estimate diffusivities ranging from 2 × 10^?22 to 5 × 10^?25 m²/s. These results are significantly lower than experimental data predict yet are consistent with other empirical data on natural titanites, suggesting that Pb diffusivity is similar to that of Sr. Thus our data challenge the wide‐held assumption that U–Pb titanite dates only reflect cooling ages.     

A Synthetic Haematite Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Application to Iron Oxide‐Cu‐Au Systems

In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe₂O₃) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe₂O₃ were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.