SA01 – A Proposed Zircon Reference Material for Microbeam U‐Pb Age and Hf‐O Isotopic Determination

A new natural zircon reference material SA01 is introduced for U‐Pb geochronology as well as O and Hf isotope geochemistry by microbeam techniques. The zircon megacryst is homogeneous with respect to U‐Pb, O and Hf isotopes based on a large number of measurements by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS). Chemical abrasion isotope dilution thermal ionisation mass spectrometry (CA‐ID‐TIMS) U‐Pb isotopic analyses produced a mean ²⁰⁶Pb/²³⁸U age of 535.08 ± 0.32 Ma (2s, n = 10). Results of SIMS and LA‐ICP‐MS analyses on individual shards are consistent with the TIMS ages within uncertainty. The δ¹⁸O value determined by laser fluorination is 6.16 ± 0.26‰ (2s, n = 14), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio determined by solution MC‐ICP‐MS is 0.282293 ± 0.000007 (2s, n = 30), which are in good agreement with the statistical mean of microbeam analyses. The megacryst is characterised by significant localised variations in Th/U ratio (0.328–4.269) and Li isotopic ratio (?5.5 to +7.9‰); the latter makes it unsuitable as a lithium isotope reference material.     

GHR1 Zircon – A New Eocene Natural Reference Material for Microbeam U‐Pb Geochronology and Hf Isotopic Analysis of Zircon

We present multitechnique U‐Pb geochronology and Hf isotopic data from zircon separated from rapakivi biotite granite within the Eocene Golden Horn batholith in Washington, USA. A weighted mean of twenty‐five Th‐corrected ²⁰⁶Pb/²³⁸U zircon dates produced at two independent laboratories using chemical abrasion‐isotope dilution‐thermal ionisation mass spectrometry (CA‐ID‐TIMS) is 48.106 ± 0.023 Ma (2s analytical including tracer uncertainties, MSWD = 1.53) and is our recommended date for GHR1 zircon. Microbeam ²⁰⁶Pb/²³⁸U dates from laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and secondary ion mass spectrometry (SIMS) laboratories are reproducible and in agreement with the CA‐ID‐TIMS date to within < 1.5%. Solution multi‐collector ICP‐MS (MC‐ICP‐MS) measurements of Hf isotopes from chemically purified aliquots of GHR1 yield a mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.283050 ± 17 (2s, n = 10), corresponding to a εHf₀ of +9.3. Hafnium isotopic measurements from two LA‐ICP‐MS laboratories are in agreement with the solution MC‐ICP‐MS value. The reproducibility of ²⁰⁶Pb/²³⁸U and ¹⁷⁶Hf/¹⁷⁷Hf ratios from GHR1 zircon across a variety of measurement techniques demonstrates their homogeneity in most grains. Additionally, the effectively limitless reserves of GHR1 material from an accessible exposure suggest that GHR1 can provide a useful reference material for U‐Pb geochronology of Cenozoic zircon and Hf isotopic measurements of zircon with radiogenic ¹⁷⁶Hf/¹⁷⁷Hf.     

Rutile R632 – A New Natural Reference Material for U‐Pb and Zr Determination

A new natural rutile reference material is presented, suitable for U‐Pb dating and Zr‐in‐rutile thermometry by microbeam methods. U‐Pb dating of rutile R632 using laser ablation ICP‐MS with both magnetic sector field and quadrupole instruments as well as isotope dilution‐thermal ionisation mass spectrometry yielded a concordia age of 496 ± 2 Ma. The high U content (> 300 μg g^?1) enabled measurement of high‐precision U‐Pb ages despite its young age. The sample was found to have a Zr content of 4294 ± 196 μg g^?1, which makes it an excellent complementary reference material for Zr‐in‐rutile thermometry. Individual rutile grains have homogeneous compositions of a number of other trace elements including V, Cr, Fe, Nb, Mo, Sn, Sb, Hf, Ta and W. This newly characterised material significantly expands the range of available rutile reference materials relevant for age and temperature determinations.     

Mud Tank Zircon: Long‐Term Evaluation of a Reference Material for U‐Pb Dating,Hf‐Isotope Analysis and Trace Element Analysis

Zircon megacrysts from the Mud Tank carbonatite, Australia, are being used in many laboratories as a reference material for LA‐ICP‐MS U‐Pb dating and trace element measurement, and LA‐MC‐ICP‐MS determination of Hf isotopes. We summarise a database of > 10000 analyses of Mud Tank zircon (MTZ), collected from 2000 to 2018 during its use as a secondary reference material for simultaneous U‐Pb and trace element analysis, and for Hf‐isotope analysis. Trace element mass fractions are highest in dark red‐brown stones and lowest in colourless and gem‐quality ones. Individual unzoned grains can be chemically homogeneous, while significant variations in trace element mass fraction are associated with oscillatory zoning. Chondrite‐normalised trace element patterns are essentially parallel over large mass fraction ranges. A Concordia age of 731.0 ± 0.2 Ma (2s, n = 2272) is taken as the age of crystallisation. Some grains show lower concordant to mildly discordant ages, probably reflecting minor Pb loss associated with cooling and the Alice Springs Orogeny (450–300 Ma). Our weighted mean ¹⁷⁶Hf/¹⁷⁷Hf is 0.282523 ± 10 (2s, n = 9350); the uncertainties on this ratio reflect some heterogeneity, mainly between grains. A few analyses suggest that colourless grains have generally lower ¹⁷⁶Hf/¹⁷⁷Hf. MTZ is a useful secondary reference material for U‐Pb and Hf‐isotope analysis, but individual grains need to be carefully selected using CL imaging and tested for homogeneity, and ideally should be standardised by solution analysis.     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).     

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).     

NanoSr – A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g^?1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g^?1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction), as well as laser ablation and solution ICP‐MS in different laboratories. The ⁸⁷Sr/⁸⁶Sr ratio was determined by well‐established bulk methods for Sr isotope measurements and is 0.70756 ± 0.00003 (2s). The Sr isotope microhomogeneity of the material was determined by LA‐MC‐ICP‐MS, which resulted in ⁸⁷Sr/⁸⁶Sr ratios of 0.70753 ± 0.00007 (2s) and 0.70757 ± 0.00006 (2s), respectively, in agreement with the solution data within uncertainties. Thus, this new reference material is well suited to monitor and correct microanalytical Sr isotope measurements of low‐Sr, low‐REE carbonate samples. NanoSr is available from the corresponding author.     

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.     

Dating Micrometre‐Thin Rims Using a LA‐ICP‐MS Depth Profiling Technique on Zircon from an Archaean Metasediment: Comparison with the SIMS Depth Profiling Method

Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) was examined as a tool for measuring isotopic variation as a function of ablation depth in unpolished zircon from an Archaean metasediment specimen. This technique was able to identify micrometre‐thin (> 3 μm) isotopically distinct mineral domains characterised by ca. 100 Myr younger ²⁰⁷Pb/²⁰⁶Pb ages associated with 2s age uncertainties as low ~ 0.2%, as well as elevated U content relative to grain interiors (up to an order of magnitude). Our calculated drilling rate suggests that each laser pulse excavated depths of ~ 0.06 μm. Ages resolved through the LA‐ICP‐MS methods overlap the 2s uncertainties of ²⁰⁷Pb/²⁰⁶Pb ages measured using SIMS depth profiling on the same zircon population. The rims were further evinced by the detection of relative enrichment (> 3 orders of magnitude) in REE in the outermost micrometres of the same zircon, measured using a different and independent LA‐ICP‐MS depth profiling technique. We propose a LA‐ICP‐MS U–Pb technique capable of quickly identifying and quantifying rims, which are indication of late, yet geologically significant, fluid events that are otherwise undefined.     

Zircon M127 – A Homogeneous Reference Material for SIMS U–Pb Geochronology Combined with Hafnium,Oxygen and,Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS‐determined mean U–Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for ²⁰⁶Pb/²³⁸U and 0.67676 ± 0.00023 for ²⁰⁷Pb/²³⁵U (weighted means, 2s uncertainties). Its ²⁰⁶Pb/²³⁸U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The δ¹⁸O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean ¹⁷⁶Hf/¹⁷⁷Hf ratio (determined by solution ICP‐MS) is 0.282396 ± 0.000004 (2s). The SIMS‐determined δ⁷Li value is ?0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 μg g^?1 Li (2s). Zircon M127 contains ~ 923 μg g^?1 U. The moderate degree of radiation damage corresponds well with the time‐integrated self‐irradiation dose of 1.82 × 10¹⁸ alpha events per gram. This observation, and the (U–Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U–Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination.     

U–Pb Zircon Age Constraining the Source and Provenance of Gem‐Bearing Late Cenozoic Detrital Deposits,Mamfe Basin,SW Cameroon

Zircons and other heavy minerals (corundum, rutile, ilmenite, magnetite, sillimanite) are identified in the Nsanaragati gem corundum placer deposit, in the western part of the Mamfe sedimentary basin, SW Cameroon. These alluvial minerals have different morphological characteristics and zircons, in particular, vary mostly in colour and shape. They are reddish, brownish, yellowish, pink or colourless. These minerals form rounded and sub‐rounded alluvial grains, prismatic, pyramidal or dipyramidal crystals. Reddish zircons retain their original crystallographic shape. Trace element and U–Pb isotopic geochemical analyses of these reddish zircons, using the LA‐ICP‐MS method give significant Hf (4576–6334 ppm), Th (46–1565 ppm) and U (66–687 ppm) contents, with Th/U ratio ranging from 0.6 to 3.0. The ²⁰⁶Pb/²³⁸U corrected mean age gave 12.39 ± 0.55 Ma, which characterizes an Upper Cenozoic (Serravallian) magmatic event. The zircons are probably sourced from a magmatic field in the South eastern boundary of the Cross River Formation. The Cameroon Volcanic Line of basaltic and alkaline lavas and intrusions which lie east of the Mamfe Basin mostly range in age from 37 Ma to <1 Ma. The zircons may also relate to the Mount Bambouto plateau lavas which lie northeast of the Mamfe sedimentary basin and have an eruptive age range of 21–14 Ma. The oldest Nsanaragati reddish zircon ages overlap within error with the end stages of the Bambouto eruptions. This eruptive or a related episode provides a potential source for megacrystic reddish zircons within the Nsanagarati placer deposit.     

The Preparation and Preliminary Characterisation of Three Synthetic Andesite Reference Glass Materials (ARM‐1, ARM‐2, ARM‐3) for In Situ Microanalysis

Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g^?1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from ⁷Li to ²³⁸U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties [2 relative standard error (RSE)] estimated in the range of 1–20%.     

Dating late Quaternary events by the combined U‐Pb LA‐ICP‐MS and (U‐Th)/He dating of zircon: A case study on Omachi Tephra suite (central Japan)

Dating of young (<1 Ma) geological events has long been a challenge for geochronologists. Combining (U‐Th)/He with U‐Pb or U‐Th‐disequilibrium dating methods offers a unique dating tool that can address this important period. We present a new methodology that combines U‐Pb LA‐ICP‐MS and (U‐Th)/He dating of zircon and use it to date two Pleistocene marker tephras (A1Pm and DPm) from the Omachi Tephra suite (Japan). A1Pm and DPm yield U‐Pb ages in the range of 350–850 and ~140–630 ka, respectively, documenting protracted periods of zircon crystallisation (100's of k.y.) prior to eruption. (U‐Th)/He ages constrain the eruption ages of the A1Pm and DPm tephras to 375 ± 13 and 97.1 ± 7.3 ka, respectively, and are in agreement with published estimates. This study demonstrates the potential of combined zircon U‐Pb LA‐ICP‐MS and (U‐Th)/He dating to constrain magmatic and eruption events in the critical ~100 ka–1 Ma interval.     

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.     

Methodology and Application of Hafnium Isotopes in Ilmenite and Rutile by MC‐ICP‐MS

The high abundances of the high field‐strength elements in ilmenite and rutile make these minerals particularly suitable for hafnium isotopic investigations. We present a technique for separating Hf by ion exchange chemistry from high‐TiO₂ (> 40% m/m) minerals to achieve precise Hf isotopic composition analyses by MC (multiple collector)‐ICP‐MS. Following digestion and conversion to chlorides, the first elution column is used to separate iron and the rare earth elements, the second column is designed to separate most of the titanium from Hf, an evaporation step using HClO₄ is then performed to remove any trace of HF in preparation for the third column, which is needed to eliminate any remaining trace of titanium. The modified chemistry helped to improve the yields from < 10 to > 78% as well as the analytical precision of the processed samples (e.g., sample 2033‐A1, ¹⁷⁶Hf/¹⁷⁷Hf = 0.282251 ± 25 before vs. 0.282225 ± 6 after). The technique was tested on a case study in which the Hf isotopic ratios of ilmenite and rutile (analysed prior to the chemistry improvement) were determined and permitted to evaluate that the origin of rutile‐bearing ilmenite deposits is from the same or similar magma than their, respectively, associated Proterozoic anorthosite massifs (Saint‐Urbain and Lac Allard) of the Grenville Province in Québec, Canada.     

Late Mesozoic Ore‐forming Events in the Ningwu Ore District,Middle‐Lower Yangtze River Polymetallic Ore Belt,East China: Evidence from Zircon U‐Pb Geochronology and Hf Isotopic Compositions of the Granodioritic Stocks

Late Mesozoic volcanic-subvolcanic rocks and related iron deposits, known as porphyry iron deposits in China, are widespread in the Ningwu ore district (Cretaceous basin) of the middle–lower Yangtze River polymetallic ore belt, East China. Two types of Late Mesozoic magmatic rocks are exposed: one is dioritic rocks closely related to iron mineralization as the hosted rock, and the other one is granodioritic (-granitic) rocks that cut the ore bodies. To understand the age of the iron mineralization and the ore-forming event, detailed zircon U-Pb dating and Hf isotope measurement were performed on granodioritic stocks in the Washan, Gaocun-Nanshan, Dongshan and Heshangqiao iron deposits in the basin. Four emplacement and crystallization (typically for zircons) ages of granodioritic rocks were measured as 126.1±0.5 Ma, 126.8±0.5 Ma, 127.3±0.5 Ma and 126.3±0.4 Ma, respectively in these four deposits, with the LA-MC-ICP-MS zircon U-Pb method. Based on the above results combined with previous dating, it is inferred that the iron deposits in the Ningwu Cretaceous basin occurred in a very short period of 131–127 Ma. In situ zircon Hf compositions of εHf(t) of the granodiorite are mainly from ?3 to ?8 and their corresponding 176Hf/177Hf ratio are from 0.28245 to 0.28265, indicating similar characteristics of dioritic rocks in the basin. We infer that granodioritic rocks occurring in the Ningwu ore district have an original relationship with dioritic rocks. These new results provide significant evidence for further study of this ore district so as to understand the ore-forming event in the study area.     

Constraining cooling histories: rutile and titanite chronology and diffusion modelling in NW Bhutan

U–Pb analyses of rutile and titanite commonly yield ages that constrain the timing of cooling rather than the timing of their crystallization. Rutile which grew at or close to peak temperature conditions in a mafic granulite, intermediate granulite and mafic amphibolite within juxtaposed litho/tectonostratigraphic units in the Greater Himalayan Sequence (GHS) of NW Bhutan yield LA–MC–ICP–MS U–Pb lower intercept cooling ages of 10.1 ± 0.4, 10.8 ± 0.1 and 10.0 ± 0.3 Ma, respectively. Numerical finite‐difference diffusion models constrained by previously published temperature–time and Pb diffusion data suggest that these ages are best explained by rapid cooling from peak temperature conditions of ～800 °C at 14 Ma in the granulite‐bearing unit and ～650 °C at 12 Ma in the amphibolite‐bearing unit. The good fit between the model and analysed ages confirms the relatively high retention of Pb in rutile suggested by the experimental data. Titanite that grew during an exhumation‐related amphibolite facies overprint on an eclogite facies mineral assemblage from the neighbouring Jomolhari Massif yields a U–Pb lower intercept cooling age of 14.6 ± 1.2 Ma. Diffusion modelling suggests that this age is too old to be consistent with the temperature–time paths inferred for the rutile‐bearing samples. Instead, the titanite age suggests cooling from ～650 °C at an earlier time of 17–15 Ma, implying that the high‐grade rocks in the Jomolhari Massif experienced a different cooling history from the rest of the GHS in NW Bhutan. Together these data show that high‐grade rocks from three apparently different structural levels of the GHS in NW Bhutan experienced rapid cooling at >40 °C Ma^?1 at varying times. The highest grade granulite facies rocks were exhumed from deeper structural levels that are not exposed, not preserved, or not yet recognized west of eastern Nepal. A progressive along‐strike change in tectonic regime, metamorphic history and/or exhumation mechanism across the orogen is implied by these thermochronologic data.     

U-Pb Age Determination for Seven Standard Zircons using Inductively Coupled Plasma–Mass Spectrometry Coupled with Frequency Quintupled Nd-YAG (λ = 213 nm) Laser Ablation System: Comparison with LA-ICP-MS Zircon Analyses with a NIST Glass Reference Material

This paper evaluates the analytical precision, accuracy and long‐term reliability of the U‐Pb age data obtained using inductively coupled plasma–mass spectrometry (ICP‐MS) with a frequency quintupled Nd‐YAG (λ = 213nm) laser ablation system. The U‐Pb age data for seven standard zircons of various ages, from 28 Ma to 2400 Ma (FCT, SL13, 91500, AS3, FC1, QGNG and PMA7) were obtained with an ablation pit size of 30 μm diameter. For ²⁰⁷Pb/²⁰⁶Pb ratio measurement, the mean isotopic ratio obtained on National Institute of Standards and Technology (NIST) SRM610 over 4 months was 0.9105 ± 0.0014 (n = 280, 95% confidence), which agrees well with the published value of 0.9096. The time‐profile of Pb/U ratios during single spot ablation showed no significant difference in shape from NIST SRM610 and 91500 zircon standards. These results encouraged the use of the glass standard as a calibration standard for the Pb/U ratio determination for zircons with shorter wavelength (λ = 213 nm) laser ablation. But ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages obtained by this method for seven zircon standards are systematically younger than the published U‐Pb ages obtained by both isotope dilution–thermal ionization mass spectrometry (ID‐TIMS) and sensitive high‐resolution ion‐microprobe (SHRIMP). Greater discrepancies (3–4% younger ages) were found for the ²⁰⁶Pb/²³⁸U ages for SL13, AS3 and 91500 zircons. The origin of the differences could be heterogeneity in Pb/U ratio on SRM610 between the different disks, but a matrix effect accuracy either in the ICP ion source or in the ablation‐transport processes of the sample aerosols cannot be neglected. When the ²⁰⁶Pb/²³⁸U (= 0.2302) newly defined in the present study is used, the measured ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²³⁵U ages for the seven zircon standards are in good agreement with those from ID‐TIMS and SHRIMP within ±2%. This suggests that SRM610 glass standard is suitable for ICP‐MS with laser ablation sampling (LA‐ICP‐MS) zircon analysis, but it is necessary to determine the correction factor for ²⁰⁶Pb/²³⁸U by measuring several zircon standards in individual laboratories.     

Metallogenic Epoch of Nonferrous Metallic and Silver Deposits in the Jiaodong Peninsula, China and its Geological Significance

As China's most important gold-producing district,the Jiaodong Peninsula also contains copper,lead-zinc,molybdenum(tungsten),and other nonferrous metal ore deposits,but the space-time and genetic relationships with gold deposits remain uncertain.To investigate the temporal relationship between these nonferrous metal and gold ore deposits,We collected the samples from a number of nonferrous metallic and silver deposits and metallogenetic rock bodies in the eastern Jiaodong Peninsula for isotopic dating.The results show that the Re-Os isotopic model ages of the Lengjia molybdenum deposit in Rongcheng range from 114.5± 1.8 Ma to 112.6± 1.5 Ma,with an average age of 113.6± 1.6Ma;the LA-ICP-MS ~(206)Pb/~(238)U ages of 33 zircons in the sericitization porphyritic monzogranite that hosts the Tongjiazhuang silver deposit in Rongcheng range between 122 Ma and 109 Ma,with a weighted mean age of 116.04± 0.95 Ma;the LA-ICP-MS ~(206)Pb/~(238)U ages of 31 zircons in the copper metallogenic pyroxene monzodiorite that hosts the Kuangbei copper deposit in Rongcheng range from126 Ma to 106 Ma,with a weighted mean age of 116.6± 1.7 Ma;and the LA-ICP-MS ~(206)Pb/~(238)U ages of19 zircons in the pyroxene monzodiorite surrounding the Dadengge gold and multimetal deposit in Weihai range from 113 Ma to 110 Ma,with a weighted mean age of 111.7± 0.6 Ma.All these results indicate that the metallogenic ages of the silver and nonferrous metallic deposits in the Jiaodong Peninsula are in a limited range from 118 Ma to 111 Ma.Previous studies have demonstrated that the isotopic ages of gold deposits in the Jiaodong Peninsula range from 123 Ma to 110 Ma,while Weideshanian magmatism occurred between 126 Ma to 108 Ma.Both these ranges are grossly consistent with the metallogenic ages of silver and nonferrous metallic deposits in this study,suggesting that the large-scale mineralization occurred in the Early Cretaceous when magmatic activities were strong.This epoch may be linked to the lithosphere thinning and the thermo-upwelling extension in eastern China at that time.In addition,field investigation also shows that gold and nonferrous metallic deposits are distributed nearby the Weideshanian granite,with the nonferrous metallic deposits lying within or surrounding the granite pluton and the gold deposits outside the granite pluton.We propose the following mineralization scenario:In the Early Cretaceous,an intensive lithospheric extension induced partial melting and degassing of the metasomatized lithospheric mantle,which resulted in the formation of mantle-derived fluids enriched in metal elements.During the rapid process of magma ascent and intrusion,crust-derived fluids were activated by the magmatic thermal dome and served to further extract ore-forming materials from the crust.These fluids may have mixed with the mantle-derived fluid to form a crust-mantle mixing-type ore-forming fluid.The high-temperature conditions in the center or in contact with the granitic magmatic thermal dome would have been favorable for the formation of porphyry-type,skarn-type,and hydrothermal-vein-type ores,thus forming a series of Mo(W),Cu,and Pb-Zn deposits in the mid-eastern Jiaodong Peninsula.In contrast,the medium-to low-temperature conditions in the periphery of the magmatic thermal dome would have favored the deposition of gold(silver) ores under the appropriate physiochemical and structural conditions.The metallogenic epoch of the molybdenum,copper,and silver deposits,and their spatio-temporal and genetic relations to the gold deposits,as demonstrated in this study,not only provide important insights to the study of regional metallogeny,our understanding of the metallogenesis of the Jiaodong type gold deposit,and the geodynamic background of the large-scale mineralization in the Jiaodong Peninsula,but also have practical value in guiding the mineral exploration.     

In situ U–Pb rutile dating by LA-ICP-MS: <Superscript>208</Superscript>Pb correction and prospects for geological applications

Rutile is a common accessory mineral that occurs in a wide spectrum of metamorphic rocks, such as in blueschists, eclogites, and granulites and as one of the most stable detrital heavy minerals in sedimentary rocks. The advent of rutile trace element thermometry has generated increased interest in a better understanding of rutile formation. This study documents important analytical advances in in situ LA-ICP-MS U/Pb geochronology of rutile: (1) Matrix matching, necessary for robust in situ dating is fulfilled by calibrating and testing several rutile standards (R10, R19, WH-1), including the presentation of new TIMS ages for the rutile standard R19 (489.5 ± 0.9 Ma; errors always stated as 2 s). (2) Initial common lead correction is routinely applied via ²⁰⁸Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb concordia ages for the two other rutile standards (493 ± 10 Ma for R19; 2640 ± 50 Ma for WH-1) and four rutile-bearing metamorphic rocks (181 ± 4 Ma for Ivrea metapelitic granulite; 339 ± 7 Ma for Saidenbach coesite eclogite; 386 ± 8 Ma for Fjortoft UHP metapelite; 606 ± 12 Ma for Andrelandia metepelitic granulite) always agree within 2% with the reported TIMS ages and other dating studies from the same localities. The power of in situ U/Pb rutile dating is illustrated by comparing ages of detrital rutile and zircon from a recent sediment from the Christie Domain of the Gawler Craton, Australia. While the U/Pb age spectrum from zircons show several pronounced peaks that are correlated with magmatic episodes, rutile U/Pb ages are marked by only one pronounced peak (at ca 1,675 Ma) interpreted to represent cooling ages of this part of the craton. Rutile thermometry of the same detrital grains indicates former granulite-facies conditions. The methods outlined in this paper should find wide application in studies that require age information of single spots, e.g., provenance studies, single-crystal zoning and texturally controlled dating.