Instrumental Mass Fractionation Research Articles

Chromite Reference Materials and Matrix Effects in SIMS Oxygen Isotope Measurements

Secondary ion mass spectrometry (SIMS) measurements of δ18O in nine chromite (Mg, Fe)(Al, Cr, Fe)2O4 samples (Cr# = 0.58–0.79, Mg# = 0.39–0.72) from chromitites and harzburgite have confirmed their intra‐ and inter‐grain isotopic homogeneity, making them suitable reference materials for in situ analysis. The SIMS measurements of the oxygen isotopic composition of these chromites exhibit a range of instrumental mass fractionation (IMF) as a function of the end‐member compositions of the chromite, particularly the magnetite (FeOFe2O3) and spinel (MgAl2O4) components. Functional relationships have been developed to correct for IMF over the compositional range XMag = 0.01 to 0.05, and XSpl = 0.14 to 0.22. We conclude that, to be accurate, SIMS measurements of δ18O must be combined with electron probe microanalyses of the individual analysed spots.

SIMS Iron Isotope Measurements of the Balmat Pyrite Reference Material: A Non‐Unique δ56Fe Signature

In situ iron isotope ratios (δ56Fe) in sulfide measured by secondary ion mass spectrometry (SIMS) can provide valuable information on several of Earth's surface processes. SIMS relies on the use of a matrix‐matched reference material to correct for instrumental mass fractionation. To date Balmat pyrite has been widely used as a reference material, on the assumption of its homogeneous δ56Fe composition. However, several studies have reported divergent bulk δ56Fe values, which may jeopardise its use. Here, we combined bulk solution MC‐ICP‐MS and in situ SIMS δ56Fe measurements on two Balmat batches: the Balmat‐Original published in Whitehouse and Fedo (2007) and Balmat‐UNIL. Despite similar compositions, this study demonstrates the existence of two isotopically distinct Balmat populations. With respect to Balmat‐Original (δ56Fe = ‐0.39 ± 0.05‰, 2s), Balmat‐UNIL is isotopically 'lighter' with a bulk solution MC‐ICP‐MS composition of ‐1.46 ± 0.024‰. Additionally, Balmat‐UNIL has two subpopulations: the first is characterised by δ56Fe values of ‐1.46 ± 0.25‰, whereas the second agrees with the original Balmat batch. In each Balmat‐UNIL subpopulation, the intra‐grain and inter‐grain variabilities are sufficient to use Balmat as a reference material for δ56Fe isotope measurements by SIMS. This study revealed at least two end‐member compositions of Balmat pyrite and calls for a careful batch‐specific determination of bulk δ56Fe.

Precise Measurement of Magnesium Isotopes in Fe‐Mg Minerals Using a Multi‐collector SHRIMP Ion Microprobe

The distribution of Mg isotopes in minerals is becoming increasingly relevant in Earth science. Usually, they are determined by dissolving mineral concentrates and, after purifying Mg with ion exchange resins, analysing the resulting solutions by TIMS or, most often, MC‐ICP‐MS. When applied to individual minerals, these methods are slow and prone to contamination from impurities in the concentrates, inconveniences that may be avoided using spot analysis techniques such as LA‐MC‐ICP‐MS or SIMS, albeit at the price of a large instrumental mass fractionation (IMF) and isobaric interferences, most prominent in the former. Here, we studied the potential of the multi‐collector SHRIMP II ion microprobe for measuring Mg isotopes in Fe‐Mg silicates and oxides. We found that, when corrected for the divergence of the Mg ion paths within the sample chamber caused by the Earth's magnetic field, the SHRIMP's IMF overwhelmingly depends on the mineral species, and the effects of variable chemical composition are negligible. We propose that the IMF is caused by the force constant difference, ∆F, between "hard" and "soft" bonds linking the ions of the studied element to the mineral lattice. Given that ∆F is a constant for each mineral species, we calculated IMF‐correction factors for the most common Mg‐bearing minerals. The thus‐calculated correction factors permit the analysis in the same session, and with reasonable accuracy (within ~ 0.3‰ of the δ26Mg determined by SN‐MC‐ICP‐MS analyses of concentrates), of samples from different mineral species, facilitating the application of Mg isotopes to terrestrial studies.

Sources of Inaccuracy in Boron Isotope Measurement Using LA‐MC‐ICP‐MS

Laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) has become a valuable tool for the in situ measurement of the boron isotope composition of geological samples at high (tens to hundreds of μm) spatial resolution. That said, this application suffers from significant analytical challenges. We focus in this study on the underlying processes of two of the main causes for inaccuracies using this technique. We provide empirical evidence that not only Ca ions (Sadekov et al. 2019, Standish et al. 2019, Evans et al. 2021) but also Ar ions, that are reflected within the flight tube of the mass spectrometer, are the source for previously reported issues with spectral baselines. We also address the impact of plasma conditions on the instrumental mass fractionation as a source for matrix‐ and mass‐load‐related analytical biases. Comparing experimental data with the results of a dedicated release and diffusion model (RDM) we estimate that a close to complete (~ 97%) release of boron from the sample aerosol is needed to allow for consistently accurate LA boron isotope measurement results without the need for corrections.

A silica-related matrix effect on NanoSIMS Li isotopic analysis of glasses and its online calibration

NanoSIMS Li isotope analysis of silicate glasses is affected by instrumental mass fractionation (IMF) due to the matrix effect. Here, we found that the IMF is correlated with the silica content and can be well corrected.

A LA‐ICP‐MS Comparison of Reference Materials Used in Cassiterite U‐Pb Geochronology

Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) is used to compare the suitability of four cassiterite (SnO2) materials (SPG, Yankee, AY‐4 and Jian‐1), and three matrix‐mismatched reference materials (NIST SRM 612, NIST SRM 614 and 91500 zircon) for normalisation of U‐Pb and Pb‐Pb isotope ratios in cassiterite. The excess variance of ages determined by LA‐ICP‐MS is estimated to be ±0.33% for 207Pb/206Pb vs. 208Pb/206Pb isochron ages and ± 1.8% and for U‐Pb ages. Incorporation of this excess variance in cassiterite ages is necessary for realistic uncertainties. 207Pb‐206Pb ages are advantageous for dating Precambrian cassiterite such as SPG compared with U‐Pb ages as matrix effect on instrumental mass fractionation of Pb isotopes are generally considered to be minor. We note minor bias in 207Pb/206Pb vs. 208Pb/206Pb isochron ages (~ 0.6%) when using either the NIST SRM 614 or 91500 zircon reference materials and emphasise the requirement for uncertainty propagation of all sources of error and reference materials with comparable U and Pb mass fraction to the cassiterite. The 238U/206Pb isotopic ratios from normalisation to matrix‐mismatched reference materials show varied results, which emphasises the need to use matrix‐matched reference materials for calculating U‐Pb ages. When cross‐calibrated against each other, LA‐ICP‐MS U‐Pb ages of the ca. 1535 Ma SPG, ca. 245 Ma Yankee and ca. 155 Ma Jian‐1 cassiterites are all consistent with their ID‐TIMS values.

NanoSIMS as an analytical tool for measuring oxygen and hydrogen isotopes in clay minerals from palaeosols: Analytical procedure and preliminary results

Oxygen and hydrogen isotope composition of neoformed clay minerals is commonly used as a palaeoclimatic proxy. Usually, sediments and rocks (including palaeosols) contain not only neoformed clay minerals, but also detrital and/or diagenetic ones. Together with the usually small size (micro- or nanometric) of the clay minerals in these materials, this can generate difficulties during isotopic analyses by conventional spectrometry. To avoid this problem, we used nanoscale secondary ion mass spectrometry (NanoSIMS) to analyse neoformed clay minerals included in palaeosol levels in early Barremian continental profiles located in NE Spain. The bottom levels of the profiles are rich in kaolinite, whereas the top levels contain smectite (beidellite-type). The isotopic compositions of pure powder standards of kaolinite and beidellite were measured in bulk by conventional mass spectrometry to obtain reference values for calibrating the instrumental mass fractionation. Two common preparation techniques for geological samples were tested (thin sections and thick polished sections), revealing that thin sections are more suitable for NanoSIMS analysis due to their lower resin content. The high spatial resolution of the instrument allowed the elemental mapping of the samples, permitting the localization of the minerals of interest and the measurement of isotopic ratios at selected points (1 x 1 μm2) within the samples. The preliminary isotopic results allowed to distinguish a decrease in the average 18O/16O and D/H ratios from the kaolinite in the bottom levels to the smectite in the top levels, reflecting a change in the climatic conditions. The average δ18O and δD values obtained for kaolinite (δ18OSMOW=18±15‰; δDSMOW=-82±36‰ and δ18OSMOW=14±4‰; δDSMOW=-97±37‰) and smectite (δ18OSMOW=13±14‰; δDSMOW=-167±87‰ and δ18OSMOW=11±6‰; δDSMOW=-180±40‰;), respectively, are consistent with the crystallization of the clays in weathering conditions. Despite the uncertainties of these preliminary isotopic measures, the results obtained allowed to estimate an average temperature for kaolinite formation of 21-22°C, and of 16-17°C for smectite. Given suitable calibration using pure isotopic standards and adequate sample preparation, NanoSIMS can thus have a great applicability in palaeoclimatic studies involving the oxygen and hydrogen isotopic composition of nanometre-sized clay minerals from palaeosols samples.

COM-1 and Hongcheon: New monazite reference materials for the microspot analysis of oxygen isotopic composition

BackgroundMonazite, a moderately common light rare earth element (LREE) and thorium phosphate mineral, has chemical, age, and isotopic characteristics that are useful in the investigation of the origin and evolution of crustal melts and fluid-rock interactions. Multiple stages of growth and partial recrystallization commonly observed in monazite inevitably require microspot chemical and isotopic analyses, for which well-characterized reference materials are essential to correct instrumental biases. In this study, we introduce new monazite reference materials COM-1 and Hongcheon for the use in the microspot analysis of oxygen isotopic composition.FindingsCOM-1 and Hongcheon were derived from a late Mesoproterozoic (~ 1080 Ma) pegmatite dyke in Colorado, USA, and a Late Triassic (~ 230 Ma) carbonatite-hosted REE ore in central Korea, respectively. The COM-1 monazite has much higher levels of Th (8.77 ± 0.56 wt.%), Si (0.82 ± 0.07 wt.%) and lower REE contents (total REE = 49.5 ± 1.2 wt.%) than does the Hongcheon monazite (Th, 0.23 ± 0.11 wt.%; Si, < 0.1 wt.%; total REE, 59.9 ± 0.7 wt.%). Their oxygen isotopic compositions (δ18OVSMOW) were determined by gas-source mass spectrometry with laser fluorination (COM-1, 6.67 ± 0.08‰; Hongcheon-1, 6.60 ± 0.02‰; Hongcheon-2, 6.08 ± 0.07‰). Oxygen isotope measurements performed by a Cameca IMS1300-HR3 ion probe showed a strong linear dependence (R2 = 0.99) of the instrumental mass fractionation on the total REE contents.ConclusionsWe characterized chemical and oxygen isotopic compositions of COM-1 and Hongcheon monazites. Their internal homogeneity in oxygen isotopic composition and chemical difference provide an efficient tool for calibrating instrumental mass fractionation occurring during secondary ion mass spectrometry analyses.

Sn Isotopic Values in Ten Geological Reference Materials by Double‐Spike MC‐ICP‐MS

The tin mass fraction and the δ120/118Sn relative to NIST SRM 3161a were measured for ten geological reference materials among which the Sn isotopic values of W‐2a, JA‐2, JG‐2, G‐2, GBW07316, NOD‐A‐1 and SGR‐1 are reported for the first time. The sample preparation procedure implemented in this study was based on acid digestion and matrix separation by two‐stage chromatographic using AG‐MP‐1 and TRU‐Spec resin. Isotopic measurements were carried out by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), using a 117Sn–119Sn double‐spike technique to correct for the instrumental mass fractionation effects. The overall precision of this method is estimated to be ± 0.03‰ (2s, n = 81) and ± 0.07‰ (2s, n = 6) for the NIST SRM 3161a and a geological reference material BHVO‐2, respectively.

Accurate and Efficient SIMS Oxygen Isotope Analysis of Composition-Variable Minerals: Online Matrix Effect Calibration for Dolomite.

High-quality oxygen isotope analysis of composition-variable minerals (e.g., ubiquitous carbonates) using secondary ion mass spectrometry (SIMS) is extremely challenging. The classical off-line procedure, which requires additional electron probe microanalyzer (EPMA) chemical compositions for calibrating instrumental mass fractionation (IMF), is inherently inaccurate and analytically inefficient. In this study, the first accurate and paired SIMS analysis of δ18O and Fe# [molar Fe/(Mg + Fe)] in dolomite is reported. Based on five newly developed dolomite O-isotopic standards with an Fe# range of 0.01-0.35 obtained by SIMS, a novel accurate and rapid online matrix effect calibration method for dolomite O-isotope analysis was developed using concurrent SIMS 18O-16O-56Fe16O-24Mg16O measurements without additional chemical electron probe microanalysis. A logistic equation was proposed as the best-fit curve to represent the δ18O matrix effect based on the 56Fe16O/24Mg16O ratios. For CTD-4 carbonatitic dolomite with variable Fe# but homogeneous oxygen isotopes, the off-line method exhibited highly variable apparent δ18O values in the range of 5.74-10.11‰. The online method yielded a homogeneous δ18O value of 7.94 ± 0.34‰ (2SD, n = 40), which is comparable with that of bulk analysis (7.94 ± 0.20‰; 2SD). Comprehensive analyses validated the online method as the best strategy for performing accurate δ18O analysis of samples with highly heterogeneous compositions. Based on its accuracy, simplicity, and economic feasibility, this method has potential applications in the analysis of composition-complex dolomites, detrital dolomites, and other precious terrestrial and extraterrestrial materials.

Mass Bias Corrections for Hydrogen and Oxygen Isotope Analysis of Tourmaline by Secondary Ion Mass Spectrometry

ABSTRACT Hydrogen (δ2H) and oxygen (δ18O) stable isotopes are used to trace fluid sources, metals, and contaminants in the environment and Earth's subsurface. Tourmaline-supergroup minerals provide an opportunity to quantify both δ2H and δ18O from the same grain using in situ analytical techniques (e.g., Secondary Ion Mass Spectrometry – SIMS). These minerals occur in a wide variety of geological environments and have a wide range of chemical compositions. However, large differences in chemical composition are problematic during SIMS analysis, as instrumental mass fractionation (IMF) often varies with the chemical composition of the mineral. Therefore, calibration models derived by analyzing tourmalines of different chemical composition must be developed for accurate analysis by SIMS. Hydrogen and oxygen isotope analysis was done on six reference tourmaline samples using a CAMECA 7f SIMS instrument operating at extreme energy filtering. Spot-to-spot repeatability for tourmalines was in the range 4–5‰ and 0.6–1.0‰ for δ2H and δ18O, respectively. There is a strong correlation between IMF and several elements (B, Si, Ca, Fe, and Fe#). Iron content is the most robust predictor of IMF, and we report two calibration curves for the correction of δ2H and δ18O measured by SIMS using reference tourmaline crystals with different Fe contents, ranging from 0.00 to 14.00 wt.% Fe. This is the first calibration curve used to correct for the fractionation of hydrogen isotope ratios in tourmaline as measured by SIMS. Tourmaline-supergroup minerals require a suite of at least three, with a range of Fe content, to ensure accurate and precise H and O analysis by SIMS. Crystallographic orientation effects were not observed for these tourmalines.

Episodic fluid flow in an eclogite-facies shear zone: Insights from Li isotope zoning in garnet

Abstract Episodic fluid overpressure and escape is invoked as a cause or consequence of many subduction-zone seismic phenomena but can be challenging to constrain in exhumed high-pressure metamorphic rocks. In situ measurements of lithium isotopes in garnet reveal evidence of episodic fluid transport in a subduction shear zone now exposed in the Monviso ophiolite (Western Alps). Garnet from an eclogite block and associated metasomatic reaction rind was analyzed by secondary ion mass spectrometry (SIMS). All analyzed garnet preserves core-rim zoning in δ7Li and large negative δ7Li excursions (NEs) in mantles. These excursions cannot be explained by instrumental mass fractionation during analysis, equilibrium fractionation, or intracrystalline diffusion of Li within garnet. Instead, NEs were produced by kinetic fractionation of Li isotopes during bulk diffusion through a pore fluid, and the fractionated isotopic compositions were incorporated into garnet by syn-diffusion growth. Disequilibrium garnet growth textures associated with negative δ7Li support this interpretation and suggest metasomatism drove rapid garnet growth. Four distinct NEs were identified requiring that at least four pulses of fluid were transported within the adjacent shear zone. This evidence of episodic fluid transport along a subduction shear zone at eclogite facies supports models of intermediate-depth seismicity that rely on cyclic fluid overpressure and escape.

A Method for Secondary Ion Mass Spectrometry Measurement of Lithium Isotopes in Garnet: The Utility of Glass Reference Materials

We present a novel method for the measurement of lithium isotopes in garnet utilising glass reference materials and secondary ion mass spectrometry (SIMS). Measured lithium isotopic compositions of natural garnets are heterogeneous, making them unreliable reference materials for in situ determination. However, SIMS lithium isotope measurements of glasses derived from these natural garnets are isotopically identical to their parent garnets and more homogeneous, demonstrating that they can be used as reliable reference materials. To characterise the composition dependence of instrumental mass fractionation (IMF), oxide and silicate powders were used to synthesise custom‐made glass reference materials (CGRMs) with garnet‐equivalent compositions. Results for six CGRMs measured by SIMS show a significant linear relationship between IMF and FeO and MnO contents. Corrections for this compositional IMF result in changes of up to 12‰ within the compositional range explored. Uncertainty in IMF‐corrected SIMS analyses with a 20 μm spot is in the range of 2.5 to 4.5‰, depending on the garnet composition and reference materials used. The method for in situ lithium isotope measurement in garnet by SIMS presented here is highly adaptable, valid across a range of Al‐rich garnet compositions, and yields spatial resolution and precision necessary to address a range of geological applications.

SIMS oxygen isotope matrix effects in silicate glasses: Quantifying the role of chemical composition

Instrumental mass fractionation (IMF) associated with Secondary Ion Mass Spectrometry (SIMS) measurements of oxygen isotope compositions in silicate glasses was studied using a set of 27 synthesized glasses spanning a compositionally broad range of six major oxides: SiO2, TiO2, Al2O3, total FeO (FeOt), MgO and CaO. The impact of chemical composition on the IMF values was investigated using a Cameca 1280-HR during a single SIMS analytical session operated under constant instrumental conditions. The data measured were compared with the δ18O values obtained by laser fluorination gas source mass-spectrometry (LF). The offset between the δ18O(LF) and δ18O(SIMS) was found to reach up to 5‰. Our data document that SIMS oxygen isotope matrix effects in silicate glasses strongly depend on the chemical composition of silicate glasses, here the cation‑oxygen bond strength was found to have a strong influence on the IMF value. We tested a variety of models based on single oxide contents and various composition-dependent parameters, but none were fully satisfactory for predicting IMF. Neither mean atomic mass nor NBO/T (the ratio of non-bridging oxygens per tetrahedrally coordinated cation) show a strong correlation with the IMF values (R2 of 0.45 and 0.46, respectively). Among the single oxides, only the model based on the SiO2 content is useful for prediction of the IMF in silicate glasses, but this model has a large standard error (1σ = ± 0.90‰) and was also found to break down for glasses with high Na and K contents. We propose an empirical model based on the correlation of six major element oxides that shows a strong correlation with IMF (R2 = 0.98, 1σ = ± 0.40‰). This model describes the experimental data with uncertainties that are roughly a factor of two better than the correction methods proposed in earlier studies. We also investigated using the correlation between IMF and isotope I-18O index, which describes the correlation between atomic bond strength and relative oxygen isotope enrichment in silicate substances (R2 = 0.87). Although our efforts provide refinements to the SIMS determination of δ18O in natural silicate glasses, truly accurate IMF corrections will need further refinements related to the impact of alkali elements.

Instrumental mass fractionation during sulfur isotope analysis by secondary ion mass spectrometry in natural and synthetic glasses

Sulfur isotope ratios are among the most commonly studied isotope systems in geochemistry. While sulfur isotope ratio analyses of materials such as bulk rock samples, gases, and sulfide grains are routinely carried out, in-situ analyses of silicate glasses such as those formed in magmatic systems are relatively scarce in the literature. Despite a number of attempts in recent years to analyse sulfur isotope ratios in volcanic and experimental glasses by secondary ion mass spectrometry (SIMS), the effects of instrumental mass fractionation (IMF) during analysis remain poorly understood. In this study we use more than 600 sulfur isotope analyses of nine different glasses to characterise the matrix effects that arise during sulfur isotope analysis of glasses by SIMS. Samples were characterised for major element composition, sulfur content, and sulfur isotope ratios by independent methods. Our glasses contain between 500 and 3400 ppm sulfur and cover a wide compositional range, including low-silica basanite, rhyolite, and phonolite, allowing us to investigate composition-dependent IMF. We use SIMS in multi-collection mode with a Faraday cup/electron multiplier detector configuration to achieve uncertainty of 0.3‰ to 2‰ (2σ) on measured δ34S. At high sulfur content, the analytical error of our SIMS analyses is similar to that of bulk analytical methods, such as gas-source isotope ratio mass spectrometry. We find IMF causes an offset of −12‰ to +1‰ between bulk sulfur isotope ratios and those measured by SIMS. Instrumental mass fractionation correlates non-linearly with glass sulfur contents and with a multivariate regression model combining glass Al, Na, and K contents. Both ln(S) and Al-Na-K models are capable of predicting IMF with good accuracy: 84% (ln(S)) and 87% (Al-Na-K) of our analyses can be reproduced within 2σ combined analytical uncertainty after a correction for composition-dependent IMF is applied. The process driving IMF is challenging to identify. The non-linear correlation between glass S content and IMF in our dataset resembles previously documented correlation between glass H2O abundance and IMF during D/H ratio analyses by SIMS, and could be attributed to changes in 32S− and 34S− ion yields with changing S content and glass composition. However, a clear correlation between S ion yields and S content cannot be identified in our dataset. We speculate that accumulation of alkalis at the SIMS crater floor may be the principal driving force of composition-dependent IMF. Nonetheless, other currently unknown factors could also influence IMF observed during S isotope ratio analyses of glasses by SIMS. Our results demonstrate that the use of multiple, well-characterised standards with a wide compositional range is required to calibrate SIMS instruments prior to sulfur isotope analyses of unknown silicate glasses. Matrix effects related to glass Al-Na-K contents are of particular importance for felsic systems, where alkali and aluminium contents can vary considerably more than in mafic magmas.

Mass fractionation of Rb and Sr isotopes during laser ablation-multicollector-ICPMS: in situ observation and correction

BackgroundOne of the most critical issues concerning in situ mass spectrometry lies in accounting for elements and molecules that overlap target isotopes of analytical interest in a sample. This study traced the instrumental mass fractionation of Rb and Sr isotopes during laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS) to obtain reliable 87Sr/86Sr ratios for high-Rb/Sr samples.FindingsIn the LA-MC-ICPMS analysis, Kr interferences were corrected using Ar and He gas blanks measured without ablating material. Contributions from doubly charged Er and Yb ions were corrected using the intensities of half masses and isotopic compositions reported in the literature. After Kr correction, the calculated 166Er2+ intensity of NIST SRM 610 approached the measured intensity at mass 83, and the 173Yb2+/171Yb2+ ratio agreed with the recommended value within error ranges. Kr- and REE2+-stripped peak intensities were further corrected for Rb interference. Use of the Sr mass bias factor for the calculation of measured 87Rb/85Rb yielded 87Sr/86Sr ratios consistent with the recommended and expected values for low-Rb/Sr materials, such as NIST SRM 616, modern shark teeth, and plagioclase collected from Jeju Island, but failed to account for the 87Rb interference from high-Rb/Sr materials including NIST SRM 610 and SRM 612. We calculated in situ mass bias factor of Rb from the known 87Sr/86Sr ratios of the standards and observed a correlation between Rb and Sr mass fractionation, which allowed inference of the Rb bias from the standard run. Reliable 87Sr/86Sr and 85Rb/86Sr ratios were obtained for SRM 610 and SRM 612 using the inferred mass bias factor of Rb calculated by the standard bracketing method.ConclusionsThis study revealed that Rb and Sr isotopes behave differently during LA-MC-ICPMS and suggests the potential usefulness of the standard bracketing method for measuring the Rb–Sr isotopic compositions of high-Rb/Sr materials.

Accurate in situ oxygen isotopic analysis at high resolution by secondary ion mass spectrometry shows the potential of aragonite as a reference material

Matrix effect in SIMS aragonite oxygen isotopic analysis.

High-spatial-resolution measurements of iron isotopes in pyrites by secondary ion mass spectrometry using the new Hyperion-II radio-frequency plasma source.

Iron isotopic signatures in pyrites are considered as a good proxy for reconstructing paleoenvironmental and local redox conditions. However, the investigation of micro-pyrites less than 20 μm in size has been limited by the available analytical techniques. The development of a new brighter radio-frequency plasma ion source (Hyperion-II source) enhances the spatial resolution by increasing the beam density 10 times compared with the Duoplasmatron source. Here we present high-spatial-resolution measurements of iron isotopes in pyrites using a 3 nA-3 μm primary 16 O- beam on two Cameca IMS 1280-HR2 ion microprobe instruments equipped with Hyperion sources at CRPG-IPNT (France) and at SwissSIMS (Switzerland). We tested analytical effects, such as topography and crystal orientation, that could induce analytical biases perceptible through variations of the instrumental mass fractionation (IMF). The δ56 Fe reproducibility for the Balmat pyrite standard is ±0.25‰ (2 standard deviations) and the typical individual internal error is ±0.10‰ (2 standard errors). The sensitivity on 56 Fe+ was 1.2 × 107  cps/nA/ppm or better. Tests on Balmat pyrites revealed that neither the crystal orientation nor channeling effects seem to significantly influence the IMF. Different pyrite standards (Balmat and SpainCR) were used to test the accuracy of the measurements. Indium mounts must be carefully prepared with a sample topography less than 2 μm, which was checked using an interferometric microscope. Such a topography is negligible for introducing change in the IMF. This new source increases the spatial resolution while maintaining the high precision of analyses and the overall stability of the measurements compared with the previous Duoplasmatron source. A reliable method was developed for performing accurate and high-resolution measurements of micrometric pyrites. The investigation of sedimentary micro-pyrites will improve our understanding of the processes and environmental conditions during pyrite precipitation, including the contribution of primary (microbial activities or abiotic reactions) and secondary (diagenesis and/or hydrothermal fluid circulation) signatures.

Strontium isotope analysis of apatite via SIMS

We report the development of a SIMS analytical method for in situ Sr isotope analysis of the mineral apatite at an analytical scale of 15 μm or less. Experiments were conducted on a series of reference apatites of widely differing Sr contents at three different mass resolution settings: low (3000), moderate (4200) and very high (16000), using a large-geometry CAMECA 1280 ion microprobe retrofitted with a HyperionTM oxygen plasma ion source. Peak-stripping algorithms tailored to the different mass-resolution settings were developed to correct for significant interferences on the target strontium isotope species in the mass spectra, namely Ca dimers, CaPO, Rb and SrH, and for instrumental mass fractionation. The most consistently accurate and precise 87Sr/86Sr ratios were achieved at the 3000 mass resolution setting with appropriate energy filtering and use of a cold trap. On average, corrected 87Sr/86Sr ratios by this method were elevated by ~0.8‰ above equivalent TIMS and solution ICPMS data, with consistent behaviour across the range of Sr concentrations. Individual spot precision of ± 0.001 to 0.004 (2SE) was achieved, depending on Sr content. The key advantages of SIMS analysis compared to existing LA-MC-ICP-MS methods are the high spatial resolution, low sample consumption, and the high mass resolution that allows for the elimination of problematic isobaric interferences. Our approach is particularly useful for the analysis of small or valuable targets, such as mineral inclusions or meteoric samples, and for apatite with high REE contents. However, the much larger volume of material consumed during LA-MC-ICP-MS analysis allows for substantially better precision than the SIMS method presented here. The highly variable trace element composition of natural apatites, involving both cationic and anionic substitutions, necessitates careful characterisation of prospective targets prior to any in situ analysis, in addition to matching to appropriate reference materials.

Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their 18O/16O and 7Li/6Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in 7Li/28Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ18O, Δ’17O and δ7Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ18O determinations, which was found to be &lt; 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.