Chad Paton

Iolite: Freeware for the visualisation and processing of mass spectrometric data

Iolite is a non-commercial software package developed to aid in the processing of inorganic mass spectrometric data, with a strong emphasis on visualisation versus time of acquisition. The goal of the software is to provide a powerful framework for data processing and interpretation, while giving users the ability to implement their own data reduction protocols. It is intended to be highly interactive, providing the user with a complete overview of the data at all stages of processing, and allowing the freedom to change parameters and reprocess data at any point. The program presents a variety of windows for the selection and viewing of data versus time, as well as features for the generation of X-Y plots, summary reports and export of data. In addition, it is capable of generating X-Y images from laser ablation rasters, and combining information from up to four separate elemental concentrations (intensities of red, green and blue, and the z-axis) in a false-colour three-dimensional image. By virtue of its underlying computing environment—Igor Pro—Iolite is capable of processing very large datasets (i.e., millions of timeslices) rapidly, and is thus ideal for the interrogation of multi-hour sessions of laser ablation data that can not be easily manipulated in conventional spreadsheet applications, for example. It is also well suited to multi-day sessions of solution-mode inductively-coupled plasma mass spectrometer (ICPMS) or thermal ionisation mass spectrometer (TIMS) data. A strong emphasis is placed on the interpolation of parameters that vary with time by a variety of user selectable methods including smoothed cubic splines. Data are processed on a timeslice-by-timeslice basis, allowing outlier rejection and calculation of statistics to be employed directly on calculated results. This approach can reduce the risk of processing biases associated with the manipulation of integrated datasets, while also allowing the implementation of more complex data reduction methods.

High-precision Mg-isotope measurements of terrestrial and extraterrestrial material by HR-MC-ICPMS—implications for the relative and absolute Mg-isotope composition of the bulk silicate Earth

We report novel methods for the chemical purification of Mg from silicate rocks by ion-exchange chromatography, and high-precision analysis of Mg-isotopes by high-resolution multiple collector inductively coupled plasma source mass spectrometry (HR-MC-ICPMS). Using these methods, we have measured the relative and absolute Mg-isotope composition of a number of terrestrial and extraterrestrial materials, including international reference rock standards as well as pure Mg standards, olivine crystals separated from a mantle-derived spinel lherzolite (J12 olivine), one enstatite chondrite, a martian shergottite and sea water samples. Repeated analyses of terrestrial and extraterrestrial samples demonstrate that it is possible to routinely measure the relative Mg-isotope composition of silicate materials with an external reproducibility of 2.5 and 20 ppm for the μ26Mg* and μ25Mg values, respectively (μ notation is the per 106 deviation from a reference material). Analyses of bulk mantle-derived rocks as well as a martian shergottite and an enstatite chondrite define a restricted range in μ25Mg of −120 ± 28 ppm (2sd) relative to the DSM-3 reference standard (μ25,26Mg = 0), suggesting that the Mg-isotope composition of inner solar system bulk planetary materials is uniform within the resolution of our analyses. We have determined the absolute Mg-isotope composition of the J12 olivine, two CI chondrites as well as the DSM-3 and Cambridge-1 reference standards using a mixed 26Mg-24Mg double-spike. The differences between the absolute 25Mg/24Mg ratios of the various materials analyzed relative to the DSM-3 standard are in excellent agreement with results obtained by the sample-standard bracketing method. Based on the averages obtained for the J12 olivine separates, we estimate the absolute Mg-isotope composition for Earths mantle – and hence that of the bulk silicate Earth – to be 25Mg/24Mg = 0.126896 ± 0.000025 and 26Mg/24Mg = 0.139652 ± 0.000033. Given the restricted range of μ25Mg obtained for bulk planetary material by the sample-standard bracketing technique and the excellent agreement between the data obtained by the relative and absolute methods, we propose that these new values represent the absolute Mg-isotope composition of the bulk inner solar system. Using the absolute Mg-isotope composition of the J12 olivine, we calculate the isotopic abundances of Mg as 24Mg = 0.789548 ± 0.000026, 25Mg = 0.100190 ± 0.000018, and 26Mg = 0.110261 ± 0.000023. Based on this result, we have calculated an atomic weight for Mg of 24.305565 ± 0.000045, which is marginally heavier than previous estimates but a factor of 10 more precise.

RAPID TIMESCALES FOR MAGMA OCEAN CRYSTALLIZATION ON THE HOWARDITE-EUCRITE-DIOGENITE PARENT BODY

Asteroid 4 Vesta has long been postulated as the source for the howardite-eucrite-diogenite (HED) achondrite meteorites. Here we show that Al-free diogenite meteorites record variability in the mass-independent abundance of 26Mg (26Mg*) that is correlated with their mineral chemistry. This suggests that these meteorites captured the Mg-isotopic evolution of a large-scale differentiating magma body with increasing 27Al/24Mg during the lifespan of the short-lived 26Al nuclide (t 1/2 ~ 730,000 yr). Thus, diogenites and eucrites represent crystallization products of a large-scale magma ocean associated with the differentiation and magmatic evolution of the HED parent body. The 26Mg* composition of the most primitive diogenites requires onset of the magma ocean crystallization within 0.6–0.4 + 0.5 Myr of solar system formation. Moreover, 26Mg* variations among diogenites and eucrites imply that near complete solidification of the HED parent body occurred within the following 2-3 Myr. Thermal models predict that such rapid cooling and magma ocean crystallization could only occur on small asteroids (<100 km), implying that 4 Vesta is not the source of the HED meteorites.

CellSpace: A module for creating spatially registered laser ablation images within the Iolite freeware environment

We present a novel approach to creating compositional images using a module created for use with the freely distributed software package Iolite. The module creates images by synchronising the state of the laser (e.g., whether the laser is firing or not) and the position on the sample, which are recorded in laser log files, with concurrently collected mass spectrometer data. When these two data sources are synchronised, mass spectrometer data which are recorded temporally can then be displayed versus ablation position (i.e., spatially). Each mass spectrometer reading is then plotted as a circular spot representing the size of the area ablated. This approach has many advantages. CellSpace takes advantage of Iolites ability to manipulate data from various mass spectrometers and to reduce data of different types. Laser ablation data can be plotted over other images, such as those produced by scanning electron microscopes, where the image has been transformed into cell coordinates using third party software. This allows the analyst to visualise laser ablation data in context and to correlate sample data from multiple sources and/or techniques. The code also has the advantage of averaging data spatially, rather than just temporally, and faithfully presents the data as a corresponding laser spot, rather than a simple rectangular pixel. Here we provide an example of a fish otolith, where trace element concentrations and Sr-isotopic compositions are overlain on microscope images, providing information on migration patterns that are applicable to population studies and fisheries conservation.

The zircon ‘matrix effect’: evidence for an ablation rate control on the accuracy of U–Pb age determinations by LA-ICP-MS

Many studies now acknowledge the occurrence of systematic discrepancies between U–Pb ages determined in zircons in situ by LA-ICP-MS and the benchmark analytical method ID-TIMS. In this study, we present detailed investigations into the ablation characteristics of zircons that suggest an underlying mechanism responsible for these age biases relative to ID-TIMS. Confocal laser scanning microscopy of laser ablation pits reveals that there are small but significant differences in the amount of material removed by the laser between different zircons. Based on numerous pit depth and LA-ICP-MS 206Pb/238U ratio measurements of a suite of natural zircon reference materials and samples, we demonstrate that a systematic age bias is strongly correlated with the offset in ablation rates between the primary reference material and sample zircons. We offer further insights concerning the effects of thermal annealing on the ablation behaviour of zircons and demonstrate that, although there is a change in laser ablation rates for annealed zircons, the variations between different zircons are not eliminated. Finally, we show that slight variations in laser focus also influence the ablation behaviour of zircons and may further degrade the accuracy of U–Pb age determinations.

182Hf–182W age dating of a 26Al-poor inclusion and implications for the origin of short-lived radioisotopes in the early Solar System

Refractory inclusions [calcium–aluminum-rich inclusions, (CAIs)] represent the oldest Solar System solids and provide information regarding the formation of the Sun and its protoplanetary disk. CAIs contain evidence of now extinct short-lived radioisotopes (e.g., 26Al, 41Ca, and 182Hf) synthesized in one or multiple stars and added to the protosolar molecular cloud before or during its collapse. Understanding how and when short-lived radioisotopes were added to the Solar System is necessary to assess their validity as chronometers and constrain the birthplace of the Sun. Whereas most CAIs formed with the canonical abundance of 26Al corresponding to 26Al/27Al of ∼5 × 10−5, rare CAIs with fractionation and unidentified nuclear isotope effects (FUN CAIs) record nucleosynthetic isotopic heterogeneity and 26Al/27Al of <5 × 10−6, possibly reflecting their formation before canonical CAIs. Thus, FUN CAIs may provide a unique window into the earliest Solar System, including the origin of short-lived radioisotopes. However, their chronology is unknown. Using the 182Hf–182W chronometer, we show that a FUN CAI recording a condensation origin from a solar gas formed coevally with canonical CAIs, but with 26Al/27Al of ∼3 × 10−6. The decoupling between 182Hf and 26Al requires distinct stellar origins: steady-state galactic stellar nucleosynthesis for 182Hf and late-stage contamination of the protosolar molecular cloud by a massive star(s) for 26Al. Admixing of stellar-derived 26Al to the protoplanetary disk occurred during the epoch of CAI formation and, therefore, the 26Al–26Mg systematics of CAIs cannot be used to define their formation interval. In contrast, our results support 182Hf homogeneity and chronological significance of the 182Hf–182W clock.

Calcium isotope measurement by combined HR-MC-ICPMS and TIMS

We report a novel approach for the chemical purification of Ca from silicate rocks by ion-exchange chromatography, and a highly-precise method for the isotopic analysis of Ca—including the smallest isotope 46Ca (0.003%)—by high-resolution multiple collector inductively coupled plasma source mass spectrometry (HR-MC-ICPMS), in combination with thermal ionization mass spectrometry (TIMS). Using this approach, we measured the Ca isotope composition of a number of terrestrial rock standards and seawater. Based on these data, we show that the non-mass-dependent abundances of μ43Ca, μ46Ca, and μ48Ca (normalized to 42Ca/44Ca) can be measured with an external reproducibility of 1.8, 45 and 12.5 ppm, respectively, when measured by HR-MC-ICPMS and μ40Ca and μ43Ca to 80 and 23 ppm, respectively, when measured by TIMS (μ notation is the per 106 deviation from the reference material). Comparison with earlier studies demonstrate that it is possible to measure the mass-dependent Ca isotope composition of terrestrial materials using HR-MC-ICPMS with an external reproducibility comparable to that typically obtained with double spike TIMS techniques. The resolution of the mass-independent 43Ca, 46Ca and 48Ca data obtained by HR-MC-ICPMS represents more than a 45-, 120-, and 18-fold improvement, respectively, relative to earlier measurements obtained by TIMS. This improvement allows for a better understanding of the mass fractionation laws responsible for the mass-dependent fractionation of Ca present in natural samples and synthetic standards. For example, the presence of an apparent excess of ∼60 ppm in the μ48Ca composition of the SRM 915a suggests that equilibrium fractionation processes have generated the mass-dependent fractionation of this material. In contrast, the absence of residual anomalies in the mass-independent composition of seawater implies that biogenic and inorganic processes of carbonate formation fractionate Ca kinetically from seawater. Finally, we note that SRM 915b has a mass-dependent and mass-independent Ca isotope composition that is within the resolution of our method identical to that of bulk silicate Earth (BSE). This observation, together with the potential heterogeneity in the 40Ca composition of the SRM 915a inferred from our measurements, suggests that the SRM 915b is a better reference material to study the Ca isotope composition of terrestrial and non-terrestrial materials.

IDENTIFICATION OF AN 84 Sr-DEPLETED CARRIER IN PRIMITIVE METEORITES AND IMPLICATIONS FOR THERMAL PROCESSING IN THE SOLAR PROTOPLANETARY DISK

The existence of correlated nucleosynthetic heterogeneities in solar system reservoirs is now well demonstrated for numerous nuclides. However, it has proven difficult to discriminate between the two disparate processes that can explain such correlated variability: incomplete mixing of presolar material or secondary processing of a well-mixed disk. Using stepwise acid-leaching of the Ivuna CI-chondrite, we show that unlike other nuclides such as 54Cr and 50Ti, Sr-isotope variability is the result of a carrier depleted in 84Sr. The carrier is most likely presolar SiC, which is known to have both high Sr-concentrations relative to solar abundances and extremely depleted 84Sr compositions. Thus, variability in 84Sr in meteorites and their components can be attributed to varying contributions from presolar SiC. The observed 84Sr excesses in calcium-aluminum refractory inclusions (CAIs) suggest their formation from an SiC-free gaseous reservoir, whereas the 84Sr depletions present in differentiated meteorites require their formation from material with an increased concentration of SiC relative to CI chondrites. The presence of a positive correlation between 84Sr and 54Cr, despite being hosted in carriers of negative and positive anomalies, respectively, is not compatible with incomplete mixing of presolar material but instead suggests that the solar systems nucleosynthetic heterogeneity reflects selective thermal processing of dust. Based on vaporization experiments of SiC under nebular conditions, the lack of SiC material in the CAI-forming gas inferred from our data requires that the duration of thermal processing of dust resulting in the vaporization of CAI precursors was extremely short-lived, possibly lasting only hours to days.

Ultra-high-precision Nd-isotope measurements of geological materials by MC-ICPMS

We report novel techniques allowing the measurement of Nd-isotope ratios with unprecedented accuracy and precision by multi-collector inductively coupled plasma mass spectrometry. Using the new protocol, we have measured the Nd-isotopic composition of rock and synthetic Nd standards as well as that of the Allende carbonaceous chondrite. Analyses of BCR-2, BHVO-2 and GSP-2 rock standards yield mass-independent compositions identical to the JNdi-1 Nd-reference standard, with an external reproducibility of 2.4, 1.6, 1.6 and 3.5 ppm respectively, on μ142Nd, μ145Nd, μ146Nd and μ150Nd (μ representing the ppm-deviation of the ratios from JNdi-1) using 148Nd/144Nd for internal normalization. This represents an improvement in precision by a factor of 2, 7 and 9 respectively for μ142Nd, μ145Nd and μ150Nd. Near-quantitative recovery from purification chemistry and sample-standard bracketing allow for the determination of mass-dependent Nd-isotopic composition of samples. Synthetic standards, namely La Jolla and AMES, record mass-dependent variability of up to 1.2 ε per atomic mass unit and mass-independent compositions resolvable by up to 3 ppm for μ142Nd and 8 ppm for μ150Nd, relative to JNdi-1. The mass-independent compositions are consistent with equilibrium mass fractionation during purification. The terrestrial rock standards define a uniform stable ε145Nd of -0.24 ± 0.19 (2SD) relative to JNdi-1, indistinguishable from the mean Allende ε145Nd of -0.19 ± 0.09. We consider this value to represent the mass-dependent Nd-isotope composition of Bulk Silicate Earth (BSE). The modest mass-dependent fractionation of JNdi-1 relative to BSE results in potential effects on mass-independent composition that cannot be resolved within the reproducibility of our analyses when correcting for natural and instrumental mass fractionation by kinetic law, making it a suitable reference standard for analysis of unknowns. Analysis of Allende (CV3) carbonaceous chondrite returns an average μ142Nd deficit of -30.1 ± 3.7 ppm in agreement with previous studies. The apparent deficit is, however, lowered to -23.8 ± 4.0 ppm while normalizing to 148Nd/144Nd instead of 146Nd/144Nd. We interpret this as the effect of a possible nucleosynthetic anomaly of -6.3 ± 0.5 ppm in μ146Nd. As 142Nd and 146Nd are both s-process-dominated nuclides, this hints at the possibility that terrestrial μ142Nd excess may not reflect 146Sm decay as widely accepted.

High-precision 27Al/24Mg ratio determination using a modified isotope-dilution approach

The precision of the 26Al–26Mg system—one of the most widely used chronometers for constraining the relative timing of events in the early solar system—is presently limited by methods for the determination of 27Al/24Mg ratios, which have seen little improvement in the last decade. We present a novel method for the measurement of 27Al/24Mg ratios in unpurified sample solutions by multiple-collector inductively coupled plasma mass spectrometry. Because Al is monoisotopic we use a modified isotope dilution approach that employs a mixed spike containing isotopically enriched 25Mg and natural 27Al in an accurately known ratio. In order to determine the spike to sample ratio for Al, measurements of spiked aliquots are bracketed by unspiked aliquots, which negates the impact of elemental bias. Unlike conventional isotope dilution, samples do not require chromatographic separation prior to analysis, which both saves time and minimises the risk of contamination of other samples with spike (which is added immediately prior to analysis). Repeat measurements of the BHVO-2, BCR-2, and BIR-1 international rock standards, as well as a gravimetrically prepared Al–Mg reference solution, indicate that our method is both accurate and reproducible to 0.2%. This 4- to 10-fold improvement over previous methods translates directly to an equal gain in the resolution of the 26Al–26Mg chronometer. The approach presented here could, in principle, be applied to other monoisotopic elements such as the Mn–Cr system. Based on multiple measurements of a ∼2.7 gram piece of the Ivuna CI chondrite, we present a new estimate for the 27Al/24Mg ratio of this meteorite of 0.09781 ± 0.00029.