Ion microprobe U–Pb dating of zircon with a 15 micrometer spatial resolution using NanoSIMS

We developed a ²³⁸U–²⁰⁶Pb^⁎ and ²⁰⁷Pb^⁎–²⁰⁶Pb^⁎ zircon dating method using a Cameca NanoSIMS NS50 ion microprobe. A 7-to 9-nA O⁻ primary beam was used to sputter a 15-μm crater, and secondary positive ions were extracted for mass analysis using the Mattauch–Herzog geometry. The multicollector system was modified to detect ⁹⁰Zr⁺, ²⁰⁴Pb⁺, ²⁰⁶Pb⁺, ²³⁸U¹⁶O⁺, and ²³⁸U¹⁶O₂⁺ ions simultaneously. A mass resolution of about 4000 at 10% peak height and with a flat peak top was attained, and the sensitivity of Pb was about 4 cps·nA^− 1·ppm^− 1. A multicrystal zircon standard (QGNG) from South Australia with a U–Pb age of 1842 Ma was used as a reference for Pb⁺/UO⁺–UO₂⁺/UO⁺ calibration, and on the basis of the positive correlation between these ratios, we determined the sample ²⁰⁶Pb/²³⁸U ratios. ²⁰⁷Pb/²⁰⁶Pb ratios were measured by magnetic scanning in single-collector mode. The standard zircons 91500, from Canada, and SL13, from Sri Lanka, were analyzed against QGNG. Observed ²³⁸U–²⁰⁶Pb^⁎ and ²⁰⁷Pb^⁎–²⁰⁶Pb^⁎ ages agreed well with published ages within experimental error. Then, 16 zircon grains in a metamorphic rock from Nagasaki, Japan, were analyzed. Observed ages were compatible with SHRIMP ages, suggesting that the NanoSIMS with a 15-μm probe diameter is suitable for ion microprobe U–Pb zircon dating.     

Origin of zircon in jadeitite from the Nishisonogi metamorphic rocks,Kyushu, Japan

On the basis of internal structures, laser ablation U–Pb ages and trace element compositions, the origin of zircon in jadeitite in the Nishisonogi metamorphic rocks was examined. The zircon comprises euhedral zoned cores overgrown by euhedral rims. The cores contain inclusions of muscovite, quartz, albite and possibly K‐feldspar, yield ²³⁸U–²⁰⁶Pb ages of 126 ± 6 Ma (±2 SD, n = 45, MSWD = 1.0), and have Th/U ratios of 0.48–1.64. The rims contain inclusions of jadeite, yield ²³⁸U–²⁰⁶Pb ages of 84 ± 6 Ma (±2 SD, n = 14, MSWD = 1.1), and have Th/U ratios of <0.06. The cores are richer in Y, Th, Ti and rare earth elements (REEs), but the rims are richer in Hf and U. Chondrite‐normalized REE patterns of the cores indicate higher Sm_N/La_N ratios, lower Yb_N/Gd_N ratios and larger positive Ce anomalies compared with those of the rims. Thus, the cores and rims have different ²³⁸U–²⁰⁶Pb ages and trace element compositions, suggesting two stages of zircon growth. Although the ²³⁸U–²⁰⁶Pb ages of the rims are consistent with the reported ⁴⁰Ar/³⁹Ar spot‐fusion ages of matrix muscovite in the jadeitite, the ²³⁸U–²⁰⁶Pb ages of the cores are older. The mineral inclusions and high Th/U ratios in the cores are best explained by crystallization from felsic magma. Therefore, the cores are considered relicts from igneous precursor rocks. The rims surrounding the inherited cores possibly precipitated from aqueous fluids during jadeitite formation. The elevated U concentrations in the rims suggest that infiltration of external fluids was responsible for the precipitation. This study provides an example of jadeitite formation by metasomatic replacement of a protolith.     

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.     

In situ U–Pb dating of micro-baddeleyite by secondary ion mass spectrometry

We introduce a technique for U–Pb dating of baddeleyite using secondary ion mass spectrometry (SIMS) in situ analysis of ng-mass crystals that cannot be efficiently extracted by conventional mineral separation techniques. Average ²⁰⁷Pb/²⁰⁶Pb ages for Precambrian baddeleyite crystals are within < 0.3% of the respective isotope dilution thermal ionization mass spectrometry (ID-TIMS) ages. ²⁰⁶Pb/²³⁸U ratios are corrected for instrumental fractionation calibrated through linear regression in a Pb/U relative sensitivity vs. UO₂⁺/U⁺ calibration plot. Calibration is performed on separated baddeleyite crystals (～ 100–200 μm in maximum dimension) mounted in random crystallographic orientation. ²⁰⁶Pb/²³⁸U ages for baddeleyite from Duluth gabbro (FC4b) and Kovdor are accurate within 1–2% when averaging 15–30 individual spot analyses and relative sensitivities calibrated on Phalaborwa baddeleyite. The relative difference of ²⁰⁶Pb/²³⁸U between large crystals and micro-baddeleyite from FC4b is within ～ 1%. Comparison between silicate glass and baddeleyite, as well as replicate analysis of the same grains in different orientations relative to the incidence direction of the primary beam support previous evidence for bias in Pb/U sensitivity in baddeleyite due to variable crystal orientations. We successfully utilized oxygen flooding and a UO₂⁺/U⁺-based calibration to significantly reduce orientation dependent bias.     

Ion microprobe U–Pb dating of zircon with a 15 micrometer spatial resolution using NanoSIMS

We developed a ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb zircon dating method using a Cameca NanoSIMS NS50 ion microprobe. A 7-to 9-nA O⁻ primary beam was used to sputter a 15-μm crater, and secondary positive ions were extracted for mass analysis using the Mattauch–Herzog geometry. The multicollector system was modified to detect ⁹⁰Zr⁺, ²⁰⁴Pb⁺, ²⁰⁶Pb⁺, ²³⁸U¹⁶O⁺, and ²³⁸U¹⁶O₂⁺ ions simultaneously. A mass resolution of about 4000 at 10% peak height and with a flat peak top was attained, and the sensitivity of Pb was about 4 cps·nA^− 1·ppm^− 1. A multicrystal zircon standard (QGNG) from South Australia with a U–Pb age of 1842 Ma was used as a reference for Pb⁺/UO⁺–UO₂⁺/UO⁺ calibration, and on the basis of the positive correlation between these ratios, we determined the sample ²⁰⁶Pb/²³⁸U ratios. ²⁰⁷Pb/²⁰⁶Pb ratios were measured by magnetic scanning in single-collector mode. The standard zircons 91500, from Canada, and SL13, from Sri Lanka, were analyzed against QGNG. Observed ²³⁸U–²⁰⁶Pb and ²⁰⁷Pb–²⁰⁶Pb ages agreed well with published ages within experimental error. Then, 16 zircon grains in a metamorphic rock from Nagasaki, Japan, were analyzed. Observed ages were compatible with SHRIMP ages, suggesting that the NanoSIMS with a 15-μm probe diameter is suitable for ion microprobe U–Pb zircon dating.     

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.     

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.     

Early Cretaceous magmatism and associated polymetallic mineralization in South China: the Tiantang example

ABSTRACT

The Tiantang Cu–Pb–Zn polymetallic deposit in western Guangdong, South China, is hosted in the contact zone between the monzogranite porphyry and limestone of the Devonian Tianziling Formation. Orebodies occur in the skarn and skarnized marble as bedded, lenses, and irregular shapes. In this study, we performed LA-ICP-MS zircon U–Pb dating, zircon trace elements, and Hf isotopic analyses on the Tiantang monzogranite porphyry closely related to Cu–Pb–Zn mineralization. Twenty-two zircons from the sample yield excellent concordia results with a weighted mean ²⁰⁶Pb/²³⁸U age of 104.5 ± 0.7 Ma, which shows that the emplacement of the monzogranite porphyry in the Tiantang deposit occurred in the Early Cretaceous. The zircon U–Pb age is largely consistent with the sulphide Rb–Sr isochron ages, indicating that both the intrusion and Cu–Pb–Zn mineralization were formed during the Early Cretaceous in South China. The ε_Hf(t) values of three inherited zircons from the monzogranite porphyry are 13.1, 11.9, and 12.9, respectively, and the two-stage Hf model ages are 1096 Ma, 1087 Ma, and 1055 Ma, respectively. Except for the three inherited zircons, all ε_Hf(t) values of zircons are negative and have a range of ?7.6 to ?3.4, with the two-stage model ages (T_DM2) of 1380–1643 Ma, which indicates the rock-forming materials were mainly derived from the partial melting of Mesoproterozoic to Neoproterozoic crust rocks, and probably included some Neoproterozoic arc-related volcanic-sedimentary materials. In this study, the monzogranite porphyry from the Tiantang deposit has calculated Ce⁴⁺/Ce³⁺ ratios of zircon ranging from 91 to 359, indicative of a more oxidized signature and significant prospecting potential for ore-related magmatism. Based on ore deposit geology, isotope geochemistry, and geochronology of the Tiantang Cu–Pb–Zn deposit and regional geodynamic evolution, the formation of Early Cretaceous magmatism and associated polymetallic mineralization in South China is believed to be related to large-scale continental extension and subsequent upwelling of the asthenosphere.     

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).     

Accuracy of Laser Ablation U-Pb Zircon Dating: Results from a Test Using Five Different Reference Zircons

Using a state‐of‐the‐art 193 nm‐LA‐MC‐ICP‐MS system and with careful control of analytical procedures, the long term external reproducibility and accuracy of the ages Phanerozoic zircons measured over a period of months using calibrator bracketing for the ²⁰⁶Pb/²³⁸U and ²⁰⁷Pb/²⁰⁶Pb ages were ca. 1% (2 RSD) if a single reference zircon was used for the matrix‐matched calibration. When different reference zircons were used for the calibration, suspicious systematic shifts in the obtained ages were observed and thus a reduction in the overall accuracy of the dating method became obvious. Such shifts were within a few percent range of the U‐Pb and Pb/Pb ages and seemed to vary independently of zircon age and composition. A “test of accuracy” experiment was conducted reducing instrumental effects as far as possible by analysing five different reference zircons mounted on a single mount eight times during the same session. An identical protocol was used for all analyses, with unchanged instrument parameters and with ion beam intensities kept as identical as possible. For data reduction, every zircon served consecutively as the reference zircon for calibration, with the others in the batch treated as unknowns. The known reference age and the four calculated ages obtained using the four other RMs for calibration were then compared. Even using such a strict analytical protocol, shifts in ²⁰⁶Pb/²³⁸U, ²⁰⁷Pb/²³⁵U and ²⁰⁷Pb/²⁰⁶Pb ratios were still present. They varied non‐systematically and ranged from ?4.35% to 3.08% for the investigated age range (1065 Ma to 226 Ma). Assuming the absence of instrumental effects (i.e., memory, dead‐time correction, non‐linearity of ion counters and interdetector calibration, crystallographic orientation, ablation cell geometry and setup, gas flows), the observed shifts were attributed to matrix and/or ablation related effects. It is proposed that non‐spectral matrix effects in the Ar plasma torch resulted in non‐uniform signal enhancement (or depression?) leading to shifts both in elemental and Pb isotopic ratios. Additionally, the ablated particle size distribution could be an important factor controlling plasma conditions and thus mass bias and fractionation. Until such effects are well understood and controlled, it would seem that any LA‐ICP‐MS zircon U‐Pb and ²⁰⁷Pb/²⁰⁶Pb age determination cannot be meaningfully interpreted at below a ca. 3% to 4% (2 RSD) confidence level.     

The giant tin polymetallic mineralization in southwest China:Integrated geochemical and isotopic constraints and implications for Cretaceous tectonomagmatic event

The Gejiu-Bozushan-Laojunshan W-Sn polymetallic metallogenic belt(GBLB) in southeast Yunnan Province is an important part of the southwestern Yangtze Block in South China.Tin polymetallic mineralization in this belt includes the Niusipo,Malage,Songshujiao,Laochang and Kafang ore fields in the Gejiu area which are spatially and temporally associated with the Kafang-Laochang and Songshujiao granite plutons.These granites are characterized by variable A/CNK values(mostly 1.1,except for two samples with 1.09),high contents of SiO_2(74.38-76.84 wt.%) and Al_2 O_3(12.46-14.05 wt.%) and variable CaO/Na_2 O ratios(0.2-0.65) as well as high zircon δ~(18)O values(7.74‰-9.86‰),indicative of S-type affinities.These rocks are depleted in Rb,Th,U,Ti,LREE[(La/Yb)N=1.4-20.51],Ba,Nb,Sr,and Ti and display strong negative Eu and Ba anomalies.The rocks possess high Rb/Sr and Rb/Ba ratios,relatively low initial ~(87)Sr/~(86)Sr ratios(0.6917-0.7101),and less radiogenic εNd(t)values(-8.0 to-9.1).The zircon grains from these rocks show negative ε_(Hf)(t) values in the range of-3.7 to-9.9 with mean T_(DM2)(Nd) and T_(DM2)(Hf) values of 1.57 Ga and 1.55 Ga.They show initial ~(207)Pb/~(204)Pb ranging from15.69 to 15.71 and ~(206)Pb/~(204)Pb from 18.36 to 18.70.Monazite from Songshujiao granites exhibits higher U and lower Th/U ratios,lower δ~(18)O values and higher ε_(Hf)(t) values than those of the zircon grains in the KafangLaochang granites.The geochemical and isotopic features indicate that the Laochang-Kafang granites originated by partial melting of Mesoproterozoic crustal components including biotite-rich metapelite and metagraywacke,whereas the Songshujiao granites were derived from Mesoproterozoic muscovite-rich metapelite crustal source.Most zircon grains from the Songshujiao,Laochang and Kafang granites have high-U concentrations and their SIMS U-Pb ages show age scatter from 81.6 Ma to 88.6 Ma,80.7 Ma to 86.1 Ma and 82.3 Ma to 87.0 Ma,suggesting formation earlier than the monazite and cassiterite.Monazite SIMS U-Pb ages and Th-Pb ages of three same granite samples are consistent and show yielded 206 Pb/~(238)U ages of 83.7 ± 0.6 Ma,83.7±0.6 Ma,and 83.4±0.6 Ma,and ~(208)Pb/~(232)Th ages of 83.2 ± 0.5 Ma,83.8 ± 0.4 Ma,and 83.5±0.9 Ma,which are within the range of the SIMS zircon U-Pb ages from these rocks.The data constrain the crystallization of the granites at ca.83 Ma.In situ U-Pb dating of two cassiterite samples from the cassiterite-sulfide ore in the Songshujiao ore field and Kafang ore field,and two from the cassiterite-oxide+cassiterite bearing dolomite in the Laochang ore field yielded weighted mean 206 Pb/~(238)U ages of 83.5±0.4 Ma(MSWD=0.6),83.5 ± 0.4 Ma(MSWD=0.5),83.6 ±0.4 Ma(MSWD=0.6) and 83.2 ±0.7 Ma(MSWD=0.6),respectively.Combined with geological characteristics,the new geochronological data indicate that the formation of the granites and Sn polymetallic deposits are coeval.We correlate the magmatic and metallogenic event with lithospheric thinning and asthenosphere upwelling in continental extension setting in relation to the eastward subduction of the Neo-Tethys beneath the Sanjiang tectonic domain during Late Cretaceous.     

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.     

Penglai Zircon Megacrysts: A Potential New Working Reference Material for Microbeam Determination of Hf–O Isotopes and U–Pb Age

We introduce a potential new working reference material – natural zircon megacrysts from an Early Pliocene alkaline basalt (from Penglai, northern Hainan Island, southern China) – for the microbeam determination of O and Hf isotopes, and U–Pb age dating. The Penglai zircon megacrysts were found to be fairly homogeneous in Hf and O isotopes based on large numbers of measurements by LA-multiple collector (MC)-ICP-MS and SIMS, respectively. Precise determinations of O isotopes by isotope ratio mass spectrometry (IRMS) and Hf isotopes by solution MC-ICP-MS were in good agreement with the statistical mean of microbeam measurements. The mean δ¹⁸O value of 5.31 ± 0.10‰ (2s) by IRMS and the mean ¹⁷⁶Hf/¹⁷⁷Hf value of 0.282906 ± 0.0000010 (2s) by solution MC-ICP-MS are the best reference values for the Penglai zircons. SIMS and isotope dilution-TIMS measurements yielded consistent ²⁰⁶Pb/²³⁸U ages within analytical uncertainties, and the preferred ²⁰⁶Pb/²³⁸U age was found to be 4.4 ± 0.1 Ma (95% confidence interval). The young age and variably high common Pb content make the Penglai zircons unsuitable as a primary U–Pb age reference material for calibration of unknown samples by microbeam analysis; however, they can be used as a secondary working reference material for quality control of U–Pb age determination for young (particularly < 10 Ma) zircon samples.     

Chronology and Geochemistry of Mesozoic Volcanic Rocks in the Linjiang Area,Jilin Province and their Tectonic Implications

Zircon U-Pb ages and geochemical analytical results are presented for the volcanic rocks of the Naozhigou, Ergulazi, and Sidaogou Formations in the Linjiang area, southeastern Jilin Province to constrain the nature of magma source and their tectonic settings. The Naozhigou Formation is composed mainly of andesite and rhyolite and its weighted mean 206Pb/238U age for 13 zircon grains is 222±1 Ma. The Ergulazi Formation consists of basaltic andesite, basaltic trachyandesite, and andesite, and six grains give a weighted mean 206Pb/238U age of 131±4 Ma. The Sidaogou Formation consists mainly of trachyandesite and rhyolite, and six zircon grains yield a weighted mean 206Pb/238U age of 113±4 Ma. The volcanic rocks have SiO2=60.24%–77.46%, MgO=0.36%–1.29% (Mg#=0.32–0.40) for the Naozhigou Formation, SiO2=51.60%–59.32%, MgO=3.70%–5.54% (Mg#=0.50–0.60) for the Ergulazi Formation, and SiO2=58.28%–76.32%, MgO=0.07%–1.20% (Mg#=0.14–0.46) for the Sidaogou Formation. The trace element analytical results indicate that these volcanic rocks are characterized by enrichment in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), relative depletion in heavy rare earth elements (HREEs) and high field strength elements (HFSEs, Nb, Ta, and Ti), and negative Eu anomalies. Compared with the primitive mantle, the Mesozoic volcanic rocks in the Linjiang area have relatively high initial 87Sr/86Sr ratios (0.7053-0.7083) and low εNd(t) values (?8.38 to ?2.43), and display an EMII trend. The late Triassic magma for the Naozhigou Formation could be derived from partial melting of a newly accretional crust with the minor involvement of the North China Craton basement and formed under an extensional environment after the collision of the Yangtze Craton and the North China Craton. The Early Cretaceous volcanic rocks for the Ergulazi and Sidaogou Formations could be formed under the tectonic setting of an active continental margin related to the westward subduction of the Izanagi plate.     

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.     

Study of melt and a clast of 546 Ma magmatic arc rocks in the 65 Ma Chicxulub bolide breccia,northern Maya block,Mexico: western limit of Ediacaran arc peripheral to northern Gondwana

The basement of the Maya block of eastern Mexico is generally covered by Mesozoic and Cenozoic platformal carbonate rocks. However, the 65.5 Ma Chicxulub meteorite impact in the northern Yucatan Peninsula excavated deep into the crust and brought crystalline basement fragments into the impact breccias. Common Pb isotopic data from impact melt and a granitic clast from drill core (Y6) are highly radiogenic, consistent with the Archaean derivation. A granodiorite clast in this breccia from drill core (Yaxcopoil-1) yielded a continuous range of concordant ²⁰⁶Pb/²³⁸U laser ablation inductively coupled plasma mass spectrometry zircon ages between 546 ± 5 Ma and 465 Ma, with three discordant zircons having ²⁰⁶Pb/²³⁸U ages between 130 Ma and 345 Ma. The ca. 546 Ma age is interpreted as the age of granodiorite intrusion, with younger ages representing variable Pb loss during melting associated with the meteorite impact. This is consistent with previous U–Pb zircon data that gave an upper intercept age of 550 ± 15 Ma at Chicxulub, which becomes 545 ± 5 Ma when combined with the zircon data from distal ejecta. Such arc rocks are absent in the southern Maya block, and in the neighbouring Oaxaquia terrane (s.s.) they are replaced by a 546 ± 5 Ma plume-related dike swarm. On the other hand, Ediacaran arc rocks continue through the peri-Gondwanan terranes of the Appalachians and Europe (Florida, Carolinia, Avalonia, Iberia, Armorica, Massif Central, Bohemia, and NW Africa). Arc magmatism in these areas ended between 570 Ma (Newfoundland) and 540 Ma (Carolinia/UK) as the subduction zone was replaced by a transform fault along the northern Gondwanan margin. This age range is synchronous with the two-stage birth of Iapetus, suggesting that both are related to major plate reorganization. The source of plume-related dikes may have been located at the rift–rift–transform triple junction between Laurentia, Baltica, and Gondwana.     

Petrogenesis of the Bao'anzhai granite and associated Mo mineralization,western Dabie orogen,east-central China: Constraints from zircon U–Pb and molybdenite Re–Os dating,whole-rock geochemistry,and Sr–Nd–Pb–Hf isotopes

Recently, many Mo deposits genetically related to emplacement of Early Cretaceous granites have been found in the Dabie–Qinling belt. A typical intrusion that combines magmatism and metallogenesis, the Bao'anzhai granite, yields a zircon ²³⁸U–²⁰⁶Pb age of 123.2 ± 1.1 Ma and a molybdenite Re–Os isochron age of 122.5 ± 2.7 Ma. This granite is characterized by high silica and alkali, but low Mg, Fe, and Ca. It is enriched with light rare earth elements (REEs) and large-ion lithophile elements (LILEs, Rb, K, Th, U) but depleted of heavy REEs, high field strength elements (HFSEs, Nb, Ta, Ti, and Y), and Sr. This high-K granite has medium initial ⁸⁷Sr/⁸⁶Sr ratios (0.706518–0.707116) and low initial Pb isotopic ratios [(²⁰⁶Pb/²⁰⁴Pb)_i, 16.423–16.699; (²⁰⁷Pb/²⁰⁴Pb)_i, 15.285–15.345; (²⁰⁸Pb/²⁰⁴Pb)_i, 37.335–37.633], and is characterized by low ?_Nd(t) and ?_Hf(t) values (?14.92 to??14.22 and??21.67 to??19.19, respectively). These data indicate that this pluton is a high-K calc-alkaline fractionated I-type granitite. It was generated by partial melting of the Yangtze lower crust, which is probably similar to Neoproterozoic TTG-like magmatic rocks at the north Yangtze Block under a non-thickened lower crust environment (<35 km). The ores also have low radiogenic Pb isotopes (²⁰⁶Pb/²⁰⁴Pb, 16.592–17.674; ²⁰⁷Pb/²⁰⁴Pb, 15.300–15.476; ²⁰⁸Pb/²⁰⁴Pb, 37.419–37.911) and low Re content in molybdenite (5.693–10.970 ppm), suggesting a crustal magmatic source for the metallogenic minerals in the Mo deposit.     

苏鲁仰口超高压岩石SHRIMP锆石U/Pb定年与部分熔融时限

在大型碰撞造山带中,在陆壳物质深俯冲或快速折返早期,在超高压-高压条件下,易熔组分可能发生水致或脱水部分熔融,形成花岗质熔体。在超高压-高压条件下,苏鲁超高压岩石发生过部分熔融作用,形成长英质多晶体包裹体和不同尺度的花岗质岩石, 导致可观的地球化学效应。为确定苏鲁超高压岩石部分熔融的时限,对山东仰口超高压副片麻岩和其中平行片麻理的同构造钾质花岗岩脉进行了SHRIMP锆石U/Pb地质年代学、全岩地球化学和锆石内矿物包裹体的研究。副片麻岩的锆石具有典型的核-幔-边结构。核部锆石为碎屑锆石,²⁰⁶Pb/²³⁸U年龄大于282Ma,可能反映了副片麻岩的原岩包含不同成因的物质;幔部和边部的Th/U比都小于0.1,分别给出233±3Ma和214±4Ma的²⁰⁶Pb/²³⁸U 年龄,分别对应于超高压变质和角闪岩相退变质年龄。同构造花岗岩脉是富钾过铝质花岗岩(A/CNK=1.2),锆石也具有核-幔-边结构;核部锆石年龄与副片麻岩的核部锆石年龄相当,反映了该花岗岩脉的源区可能是变沉积岩;除幔部锆石的一个点具有²⁰⁶Pb/²³⁸U年龄为234.6±3.9Ma之外,其它幔部锆石位于谐和线附近,给出²⁰⁶Pb/²³⁸U年龄为220.8±2.9Ma, 该年龄代表着该花岗岩脉的形成年龄。上述数据表明,在仰口地区,超高压岩石的部分熔融作用早于角闪岩相退变质作用。     

Petrogenesis of metatexite and diatexite migmatites determined using zircon U–Pb age,trace element and Hf isotope data,Higo metamorphic terrane,central Kyushu,Japan

Metatexite and diatexite migmatites are widely distributed within the upper amphibolite and granulite facies zones of the Higo low‐P/high‐T metamorphic terrane. Here, we report data from an outcrop in the highest grade part of the granulite facies zone, in which diatexite occurs as a 3 m thick layer between 2 m thick layers of stromatic‐structured metatexite within pelitic gneiss. The migmatites and gneiss contain the same peak mineral assemblage of biotite + plagioclase + quartz + garnet + K‐feldspar with retrograde chlorite ± muscovite and some accessory minerals of ilmenite ± rutile ± titanite + apatite + zircon + monazite ± pyrite ± zinc sulphide ± calcite. Calculated metamorphic P–T conditions are 800–900 °C and 9–12 kbar. Zircon in the diatexite forms elongate euhedral crystals with oscillatory zoning, but no core–rim structure. Zircon from the gneiss and metatexite forms euhedral–subhedral grains comprising inherited cores overgrown by thin rims. The overgrowth rims in the metatexite have lower Th/U ratios than zircon in the diatexite and yield a ²⁰⁶Pb/²³⁸U age of 116.0 ± 1.6 Ma, which is older than the 110.1 ± 0.6 Ma ²⁰⁶Pb/²³⁸U age derived from zircon in the diatexite. Zircon from the diatexite has variable REE contents with convex upward patterns and flat normalized HREE, whereas the overgrowth rims in the metatexite and gneiss have steep HREE‐enriched patterns; however, both types have similar positive Ce and negative Eu anomalies. ¹⁷⁶Hf/¹⁷⁷Hf ratios in the overgrowth rims from the metatexite are more variable and generally lower than values from zircon in the diatexite. Based on U–Pb ages, trace element and Hf isotope data, the zircon rims in the metatexite are interpreted to have crystallized from a locally derived melt, following partial dissolution of inherited protolith zircon during anatexis, whereas the zircon in the diatexite is interpreted to have crystallized from a melt that included an externally derived component. By integrating zircon and petrographic data for the migmatites and pelitic gneiss, the metatexite migmatite is interpreted to have formed by in situ partial melting in which the melt did not migrate from the source, whereas the diatexite migmatite included an externally derived juvenile component. The Cretaceous high‐temperature metamorphism of the Higo metamorphic terrane is interpreted to reflect emplacement of mantle‐derived basalts under a volcanic arc along the eastern margin of the Eurasian continent and advection of heat via hybrid silicic melts from the lower crust. Post‐peak crystallization of anatectic melts in a high‐T region at mid‐crustal depths occurred in the interval c. 116–110 Ma, as indicated by the difference in zircon ages from the metatexite and diatexite migmatites.     

Incorporation of U,Pb and Rare Earth Elements in Calcite through Crystallisation from Amorphous Calcium Carbonate: Simple Preparation of Reference Materials for Microanalysis

Uncertainty for elemental and isotopic measurements in calcite by LA‐ICP‐MS is largely controlled by the homogeneity of the reference materials (RMs) used for calibration and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb and rare earth elements into calcite through heat‐ and pressure‐induced crystallisation from amorphous calcium carbonate that was precipitated from element‐doped reagent solution. X‐ray absorption spectra showed that U was present as U(VI) in the synthesised calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison with synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The ²⁰⁷Pb/²⁰⁶Pb ratio in the calcite showed < 1% variations, while the ²³⁸U/²⁰⁶Pb ratio showed 3–24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC‐1, with analytical uncertainty as low as < 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions and is a promising alternative to natural calcite RMs for U‐Pb geochronology.