Sub-Micrometre Resolution FIB-SEM-based ToF-SIMS Used to Map Geochemical Zoning in Four Zircon Reference Materials

Zircon geochemistry can vary over micrometre scales; therefore, natural reference materials need to be well characterised before being used to calculate trace element mass fractions in unmeasured samples. Moreover, reference material homogeneity needs to be ensured with the accelerating rate of geoanalytical developments to map mineral chemistry at increasingly finer scales. Here, we investigate trace element zoning in four widely used zircon reference materials: 91500, Mud Tank, Temora and Plešovice, as well as zircon crystals from the Mount Dromedary/Gulaga Igneous Complex, Australia. Sub-micrometre resolution focused ion beam scanning electron microscope (FIB-SEM) based time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 5 μm resolution LA-ICP-MS mapping show that trace elements are zoned in all reference materials, though 91500 exhibited the least zonation. We demonstrate that FIB-SEM-based ToF-SIMS can rapidly resolve variations in trace elements (e.g., U, Th, Sc, Y, Gd, Dy, Yb and Li) at sensitivities down to the μg g^-1 level with a spatial resolution of 195 nm for areas 100 × 85 μm to 959 × 828 μm. Zircon 91500 is recommended for future quantitative analyses provided that (1) the spatial distribution of elements is imaged before analysis of unknown samples and (2) it is used in conjunction with a doped glass as the primary reference material.     

LA-ICP-MS锆石微区U-Pb定年方法及不同束斑直径对年龄结果的影响作用探讨

利用自然资源部古地磁与古构造重建重点实验室新引进的GeoLas HD型193nm ArF准分子激光剥蚀系统和Agilent 7900型四极杆电感耦合等离子质谱仪,成功建立了LA-ICP-MS锆石微区U-Pb定年及微量元素分析测试方法。以标准锆石91500为外标,在32 μm束斑直径、5.0 J/cm2能量密度和5 Hz剥蚀频率等实验条件下,对Ple?ovice、Temora1和Qinghu锆石标样开展了U-Pb定年实验,所测年龄结果与各标样推荐值在误差范围允许的条件下一致,并且Ple?ovice年龄结果在不同时间段内保持稳定。同时对未知年龄样品11-5开展了不同实验室测年结果对比研究,所测结果与中国地质大学(武汉)地质过程与矿产资源国家重点实验室所测年龄在误差允许范围内一致。以NIST SRM 610为外标,29Si为内标,分析测试了锆石91500和NIST SRM 612标准样品的微量元素含量,实验测试结果与推荐值一致。在此基础上探索总结了不同剥蚀斑束直径对U-Pb年龄结果的影响,认为在同样的能量密度和剥蚀频率条件下,16~44 μm的剥蚀直径可以获取可靠的锆石U-Pb年龄,但32~44 μm相比16~24 μm小斑束直径所测得的年龄更加精准。      

锆石Hf同位素组成的LA-MC-ICP-MS测定

利用多接收器等离子体质谱仪(MC-ICPMS)和193nm准分子激光器联用技术,对GJ-1、Temora、91500和Mud Tank四个标准锆石的Hf同位素组成进行测试,并通过指数方法进行同质异位素干扰校正,测得它们的176Hf/177Hf比值分别为0.282006±24(n=159, 2SD)、0.282684±46(n=20, 2SD)、0.282305±32(n=20, 2SD)和0.282509±25(n=48, 2SD)。测定结果与文献报道的值在误差范围内一致。     

Simultaneous determinations of U–Pb age,Hf isotopes and trace element compositions of zircon by excimer laser-ablation quadrupole and multiple-collector ICP-MS

We describe an in situ method for simultaneous measurement of U–Pb–Hf isotopes and trace element compositions of zircons using a quadrupole and multiple-collector inductively-coupled-plasma mass spectrometer (Q-ICP-MS and MC-ICP-MS, respectively) connected to a single excimer laser-ablation system. A laser-generated zircon aerosol was split behind the ablation cell into two transport tubes via a Y-shaped connector and simultaneously introduced into the two mass spectrometers. Hafnium isotopes were measured on the MC-ICP-MS instrument, while U–Pb ages and trace element compositions were determined using the Q-ICP-MS. The precision and accuracy of this method was evaluated using six well-known and widely used zircon standards (91500, Temora-2, GJ-1, Mud Tank, BR266 and Monastery). Analyses were carried out using spot sizes of 32, 44 and 60 μm. For the 44 and 60 μm spot, the resulting U–Pb ages, Hf isotopic and rare earth element (REE) compositions of these six zircons agree with recommended/reported values within 2σ error. The difference in relative standard deviations (RSD) of ²⁰⁶Pb/²³⁸U ages between split-flow measurements and those obtained separately on the Q-ICP-MS is within ～ 20% for 91500, Temora-2 and GJ-1, and ～ 60% for Mud Tank (due to its lower U and Pb concentrations). Our method provides a precise approach for determining the U–Pb age and the Hf isotopic and trace element compositions of zircon within a single ablation event. This is in particular important for analysis of zircons that are small or contain complicated zoning patterns. Finally, the REE composition of zircon BR266 is more homogeneous than other zircons and could be a suitable standard by which to benchmark new standards for microprobe analyses of zircons.     

VizualAge: A Novel Approach to Laser Ablation ICP‐MS U‐Pb Geochronology Data Reduction

VizualAge, a new computer software tool for analysing U‐Pb data obtained by laser ablation‐inductively coupled plasma‐mass spectrometry, was developed. It consists of a data reduction scheme (DRS) for Iolite (a general mass spectrometry data analysis tool) as well as visualisation routines. In addition to the U/Pb and Th/Pb ages calculated by Iolite’s U‐Pb geochronology DRS, VizualAge also calculates ²⁰⁷Pb/²⁰⁶Pb ages and common Pb corrections for each time‐slice of raw data. Importantly, VizualAge allows one to display a live concordia diagram for visualising data on such a diagram as an integration interval is being adjusted. This provides instantaneous feedback regarding discordance, uncertainty, error correlation and common Pb. Several zircon data sets were used to illustrate how the live concordia could be used as a powerful inspection tool, revealing a single analysis to consist of zones of concordance, metamict areas, as well as inherited cores or younger overgrowths. VizualAge also constructs histograms, conventional and Tera‐Wasserburg type concordia diagrams, as well as 3D U‐Th‐Pb and total U‐Pb concordia diagrams. The precision and accuracy of data reduced with VizualAge are demonstrated with examples of the Ple?ovice, Temora‐2 and Penglai zircon reference materials. Data for zircon from the Long Lake Batholith (Wyoming craton) were used to illustrate how VizualAge calculated common Pb corrections and helped to expose as yet unexplained difficulties with accurately determining ²⁰⁴Pb.     

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.     

SIMS Bias on Isotope Ratios in Ca‐Mg‐Fe Carbonates (Part III): δ18O and δ13C Matrix Effects Along the Magnesite–Siderite Solid‐Solution Series

This study explores the effects of cation composition on mass bias (i.e., the matrix effect), which is a major component of instrumental mass fractionation (IMF) in the microanalyses of δ¹³C and δ¹⁸O by SIMS in carbonates of the magnesite–siderite solid‐solution series (MgCO₃–FeCO₃). A suite of twelve calibration reference materials (RMs) was developed and documented (calibrated range: Fe# = 0.002–0.997, where Fe# = molar Fe/[Mg + Fe]), along with empirical expressions for regressing calibration data (affording residuals < 0.5‰ relative to certified reference material NIST‐19). The calibration curves of both isotope systems are non‐linear and have, over a 2‐year period, fallen into one of two distinct but largely self‐consistent shape categories (data from ten measurement sessions), despite adherence to well‐established analytical protocols for carbonate δ¹³C and δ¹⁸O analyses at WiscSIMS (CAMECA IMS 1280). Mass bias was consistently most sensitive to changes in composition near the magnesite end‐member (Fe# 0–0.2), deviating by up to 4.5‰ (δ¹³C) and 14‰ (δ¹⁸O) with increasing Fe content. The cause of variability in calibration curve shapes is not well understood at present and demonstrates the importance of having available a sufficient number of well‐characterised RMs so that potential complexities of curvature can be adequately delineated and accounted for on a session‐by‐session basis.     

Barium Isotopic Compositions in Thirty‐Four Geological Reference Materials Analysed by MC‐ICP‐MS

Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g^?1, SiO₂ from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ^138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ^138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ^138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.     

Matrix Corrections and Error Analysis in High‐Precision SIMS 18O/16O Measurements of Ca–Mg–Fe Garnet

We report technical and data treatment methods for making accurate, high‐precision measurements of ¹⁸O/¹⁶O in Ca–Mg–Fe garnet utilising the Cameca IMS 1280 multi‐collector ion microprobe. Matrix effects were similar to those shown by previous work, whereby Ca abundance is correlated with instrumental mass fractionation (IMF). After correction for this effect, there appeared to be no significant secondary effect associated with Mg/Fe²⁺ for routine operational conditions. In contrast, investigation of the IMF associated with Mn‐ or Cr‐rich garnet showed that these substitutions are significant and require a more complex calibration scheme. The Ca‐related calibration applied to low‐Cr, low‐Mn garnet was reproducible across different sample mounts and under a range of instrument settings and therefore should be applicable to similar instruments of this type. The repeatability of the measurements was often better than ± 0.2‰ (2s), a precision that is similar to the repeatability of bulk techniques. At this precision, the uncertainties due to spot‐to‐spot repeatability were at the same magnitude as those associated with matrix corrections (± 0.1–0.3‰) and the uncertainties in reference materials (± 0.1–0.2‰). Therefore, it is necessary to accurately estimate and propagate uncertainties associated with these parameters – in some cases, uncertainties in reference materials or matrix corrections dominate the uncertainty budget.     

The origin of variable-δ18O zircons in Jurassic and Cretaceous Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt,Northeast China

This study reports new zircon U–Pb ages, Lu–Hf isotope data, and oxygen isotope data for Mesozoic Mo-bearing granitoids in the eastern Xing–Meng Orogenic Belt (XMOB) of Northeast China, within the eastern Central Asian Orogenic Belt. Combining these new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U–Pb ages with the results of previous research indicates that two stages of Mo-bearing granitoid magmatism occurred in the eastern XMOB, during the Early–Middle Jurassic (200–165 Ma) and the Early Cretaceous (ca. 111 Ma). The eastern XMOB also contains Mo-bearing granitoids with variable δ¹⁸O compositions that record variations in source oxygen isotopic compositions. Combining δ¹⁸O data with zircon U–Pb and Hf isotopic data provides evidence of the origin of these granitoids. Three types of zircon have been identified within these granitoids. Type 1 zircons formed during the Mesozoic and having high δ¹⁸O values (5.71–7.05‰) that are consistent with the compositions of magmatic zircons from the Luming, Jiapigou, and Kanchuangou areas. These zircons suggest that the Mo-bearing granitoids were derived from a source containing supracrustal materials. The type 2 zircons have extremely low and heterogeneous δ¹⁸O values (4.64–4.89‰) that are consistent with the compositions of magmatic zircons from the Jidetun and Fuanpu areas. These magmas were generated by the remelting of juvenile crustal material that was previously significantly modified by interaction with fluids. Type 3 zircons generally have mantle-like δ¹⁸O values (5.42–5.57‰), with several zircons yielding higher δ¹⁸O values, suggesting that these intrusions formed from mantle-derived magmas that assimilated and were metasomatized by crustal material. Combining these geochemical data with the geology of this region indicates that the Mo-bearing granitoids were generated as a result of subduction of the Palaeo-Pacific Plate beneath the Eurasian continent.     

Sub‐mantle δ18O Zircons in Malani rhyolites: Clues for a Rodinia Linkage between South China and NW India

The Malani Igneous Suite (MIS) in NW India represents one of the largest and well‐preserved Precambrian felsic igneous provinces, with minor mafic volcanics and dykes. The SIMS (Secondary Ion Mass Spectrometric) zircon U‐Pb geochronology yielded 776.8 ± 4.5 to 758.5 ± 6.9 Ma ages for rhyolites from Jodhpur region and Sindreth Basin while dacite sample from Punagarh Basin was dated to 760.5 ± 10 Ma. Zircons from rhyolitic and dacitic lavas have oxygen isotopic compositions that can be grouped into low δ¹⁸OV‐SMOW (4.12 to ‐1.11‰) and high (δ¹⁸O = 8.23‐5.12‰) categoroes, respectively. The low δ¹⁸O zircons have highly radiogenic Hf isotopic compositions (ε_Hf(t)= +13.0 to +3.6) suggesting high temperature bulk cannibalization of upper level juvenile crust as the essential process for magma generation. Older than 800 Ma xenocrystic zircons in dacite have high δ¹⁸O values whereas 795 Ma ones have mantle‐like Hf‐O isotopic compositions, reflecting a significant shift in tectono‐thermal regime in NW India during 800‐780 Ma. A synchronous transition in the South China Block and Madagascar suggests a spatially and temporally linked geodynamic system. Geochemical data in combination with the new isotopic results point towards an overall convergent plate margin setting undergoing localized lithospheric extension. The NW India and South China blocks together with Madagascar and the Seychelles lay either along the periphery of Rodinia or off the supercontinent with the age of convergent plate margin magmatism coinciding with breakup of the supercontinent.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Precise Determination of Silicon Isotopes in Silicate Rock Reference Materials by MC‐ICP‐MS

A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g^‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ³⁰Si and δ²⁹Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ³⁰Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ²⁹Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ³⁰Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ³⁰Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Mg Isotope Interlaboratory Comparison of Reference Materials from Earth‐Surface Low‐Temperature Environments

To enable quality control of measurement procedures for determinations of Mg isotope amount ratios, expressed as δ²⁶Mg and δ²⁵Mg values, in Earth‐surface studies, the δ²⁶Mg and δ²⁵Mg values of eight reference materials (RMs) were determined by interlaboratory comparison between five laboratories and considering published data, if available. These matrix RMs, including river water SLRS‐5, spring water NIST SRM 1640a, Dead Sea brine DSW‐1, dolomites JDo‐1 and BCS‐CRM 512, limestone BCS‐CRM 513, soil NIST SRM 2709a and vegetation NIST SRM 1515, are representative of a wide range of Earth‐surface materials from low‐temperature environments. The interlaboratory variability, 2s (twice the standard deviation), of all eight RMs ranges from 0.05 to 0.17‰ in δ²⁶Mg. Thus, it is suggested that all these materials are suitable for validation of δ²⁶Mg and δ²⁵Mg determinations in Earth‐surface geochemical studies.     

High‐Precision Iron Isotope Analysis of Geological Reference Materials by High‐Resolution MC‐ICP‐MS

We report high‐precision iron isotopic data for twenty‐two commercially available geological reference materials, including silicates, carbonatite, shale, carbonate and clay. Accuracy was checked by analyses of synthetic solutions with known Fe isotopic compositions but different matrices ranging from felsic to ultramafic igneous rocks, high Ca and low Fe limestone, to samples enriched in transition group elements (e.g., Cu, Co and Ni). Analyses over a 2‐year period of these synthetic samples and pure Fe solutions that were processed through the whole chemistry procedure yielded an average δ⁵⁶Fe value of ?0.001 ± 0.025‰ (2s, n = 74), identical to the expected true value of 0. This demonstrates a long‐term reproducibility and accuracy of < 0.03‰ for determination of ⁵⁶Fe/⁵⁴Fe ratios. Reproducibility and accuracy were further confirmed by replicate measurements of the twenty‐two RMs, which yielded results that perfectly match the mean values of published data within quoted uncertainties. New recommended values and associated uncertainties are presented for interlaboratory calibration in the future.     

Unusual Uranium‐rich Fluid Flow During Exhumation of Deeply Subducted Continental Crust

In‐situ SIMS analyses of O and U‐Pb isotopes were carried out for zircons from a quartz vein hosted by ultrahigh‐pressure metagranite (UHP) in the Dabie orogen. The results are integrated to decipher the property of unusual U‐rich aqueous fluids and their effects on both metamorphic and magmatic zircons during exhumation of the UHP metagranite. In CL images, most zircon grains show distinct core‐rim structures. Relict cores are bright and exhibit oscillatory or patchy zonation, giving Neoproterozoic upper‐intercept ages of 795 ± 26 Ma. Newly grown rims are dark and exhibit no zoning, yielding Triassic concordant ages of 215 ± 5 Ma. The cores give Th contents of 59 to 463 ppm and U contents of 98 to 558 ppm, with Th/U ratios of 0.263 to 1.423. The rims yield reduced Th contents of 11 to 124 ppm but significantly elevated U contents of 1051 to 3531 ppm, with Th/U ratios of 0.010 to 0.035. Comparison with the cores of magmatic origin, the unusual enrichment in U but depletion in Th in the rims of metamorphic origin are interpreted as zircon growth from Cl‐rich oxidized vein‐forming aqueous fluids that were produced by dehydration reactions of the wallrock during continental exhumation. The cores have variably positive δ¹⁸O values with concordant or discordant Neoproterozoic U‐Pb ages, suggesting their solid‐state modification of both O and U‐Pb isotopes through interaction with the fluids. The rims yield negative δ¹⁸O values, indicating their growth from the negative δ¹⁸O fluids. Taken together, the proposed Cl‐rich oxidized negative‐δ¹⁸O vein‐forming aqueous fluids have such an ability to not only cause variable metamorphic recrystallization in the relict magmatic zircons but also produce dramatic fractionation of U over Th in the metamorphic zircons during quartz veining, and potentially impact on the overlain metasomatite in the mantle wedge.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part I: δ18O Matrix Effects

We document the development of a suite of carbonate mineral reference materials for calibrating SIMS determinations of δ¹⁸O in samples with compositions along the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂]. Under routine operating conditions for the analysis of carbonates for δ¹⁸O with a CAMECA IMS 1280 instrument (at WiscSIMS, University of Wisconsin‐Madison), the magnitude of instrumental bias along the dolomite–ankerite series decreased exponentially by ~ 10‰ with increasing Fe content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mol% Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the sample matrix effect) was calibrated using the Hill equation, which relates bias to the Fe# of dolomite–ankerite [i.e., molar Fe/(Mg+Fe)] for thirteen reference materials (Fe# = 0.004–0.789); for calibrations employing either 10 or 3 μm diameter spot size measurements, this yielded residual values ≤ 0.3–0.4‰ relative to CRM NBS 19 for most reference materials in the suite. Analytical precision was ± 0.3‰ (2s, standard deviations) for 10‐μm spots and ± 0.7‰ (2s) for 3‐μm spots, based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses. Analytical uncertainty for individual sample analyses was approximated by a combination of precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 0.5‰ (2s) for 10‐μm spots and ± 1‰ (2s) for 3‐μm spots.     

Correlated δ18O and [Ti] in lunar zircons: a terrestrial perspective for magma temperatures and water content on the Moon

Zircon grains were separated from lunar regolith and rocks returned from four Apollo landing sites, and analyzed in situ by secondary ion mass spectrometry. Many regolith zircons preserve magmatic δ¹⁸O and trace element compositions and, although out of petrologic context, represent a relatively unexplored resource for study of the Moon and possibly other bodies in the solar system. The combination of oxygen isotope ratios and [Ti] provides a unique geochemical signature that identifies zircons from the Moon. The oxygen isotope ratios of lunar zircons are remarkably constant and unexpectedly higher in δ¹⁸O (5.61 ± 0.07 ‰ VSMOW) than zircons from Earth’s oceanic crust (5.20 ± 0.03 ‰) even though mare basalt whole-rock samples are nearly the same in δ¹⁸O as oceanic basalts on Earth (~5.6 ‰). Thus, the average fractionation of oxygen isotopes between primitive basalt and zircon is smaller on the Moon [Δ¹⁸O(WR-Zrc) = 0.08 ± 0.09 ‰] than on Earth (0.37 ± 0.04 ‰). The smaller fractionations on the Moon suggest higher temperatures of zircon crystallization in lunar magmas and are consistent with higher [Ti] in lunar zircons. Phase equilibria estimates also indicate high temperatures for lunar magmas, but not specifically for evolved zircon-forming melts. If the solidus temperature of a given magma is a function of its water content, then so is the crystallization temperature of any zircon forming in that melt. The systematic nature of O and Ti data for lunar zircons suggests a model based on the following observations. Many of the analyzed lunar zircons are likely from K, rare earth elements, P (KREEP)-Zr-rich magmas. Zircon does not saturate in normal mafic magmas; igneous zircons in mafic rocks are typically late and formed in the last most evolved portion of melts. Even if initial bulk water content is moderately low, the late zircon-forming melt can concentrate water locally. In general, water lowers crystallization temperatures, in which case late igneous zircon can form at significantly lower temperatures than the solidus inferred for a bulk-rock composition. Although lunar basalts could readily lose H₂ to space during eruption, lowering water fugacity; the morphology, large size, and presence in plutonic rocks suggest that many zircons crystallized at depths that retarded degassing. In this case, the crystallization temperatures of zircons are a sensitive monitor of the water content of the parental magma as well as the evolved zircon-forming melt. If the smaller Δ¹⁸O(zircon–mare basalt) values reported here are characteristic of the Moon, then that would suggest that even highly evolved zircon-forming magmas on the Moon crystallized at higher temperature than similar magmas on Earth and that magmas, though not necessarily water-free, were generally drier on the Moon.     

Polymetamorphism of the Chupa Sequence of the Belomorian mobile belt (Fennoscandia): Evidence from the isotope-geochemical (U-Pb,REE, O) study of zircon

U-Pb age and isotope-geochemical features were determined for zircon from kyanite gneisses and amphibolites of the Chupa Sequence of the Belomorian mobile belt (BMB) of the Fennoscandian shield. The cores of the zircon from the gneisses marks the Neoarchean events within 2700–2800 Ma known in the BMB, while those of the amphibolites correspond to the age of magmatic crystallization (2775 ± 12 Ma). The inner rims of zircon from the amphibolites and gneisses likely record two different Neoarchean metamorphic events (2650 ± 8 and 2599 ± 10 Ma, respectively). The outer rims record Paleoproterozoic metamorphism with an age of 1890 Ma, which formed the modern appearance and mineral assemblages of the rock association. The value of δ18O in the zircon from the gneiss is 8.6‰ in cores, slightly decreases to 8.0‰ in inner rims, and sharply decreases to 3.9‰ in outer rims. The value of δ¹⁸O in the zircon from the amphibolite is around 6.2‰ in cores, increases up to 8.6 in inner rims, and decreases to 5.2‰ in outer rims. A significant decrease of δ¹⁸O is likely related to the anomalous composition of Svecofennian metamorphic fluid restricted to local shear zones. The geochemical features of the zircons in combination with their morphology and anatomy make it possible to distinguish zircon generations of different age and change in metamorphic environments.