Three-dimensional calibration surfaces, along with downhole fractionation corrections, can provide improved accuracy for trace element concentration analysis by LA-ICP-MS.
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.
Elemental fractionation effects during analysis are the most significant impediment to obtaining precise and accurate U‐Pb ages by laser ablation ICPMS. Several methods have been proposed to minimize the degree of downhole fractionation, typically by rastering or limiting acquisition to relatively short intervals of time, but these compromise minimum target size or the temporal resolution of data. Alternatively, other methods have been developed which attempt to correct for the effects of downhole elemental fractionation. A common feature of all these techniques, however, is that they impose an expected model of elemental fractionation behavior; thus, any variance in actual fractionation response between laboratories, mineral types, or matrix types cannot be easily accommodated. Here we investigate an alternate approach that aims to reverse the problem by first observing the elemental fractionation response and then applying an appropriate (and often unique) model to the data. This approach has the versatility to treat data from any laboratory, regardless of the expression of downhole fractionation under any given set of analytical conditions. We demonstrate that the use of more complex models of elemental fractionation such as exponential curves and smoothed cubic splines can efficiently correct complex fractionation trends, allowing detection of spatial heterogeneities, while simultaneously maintaining data quality. We present a data reduction module for use with the Iolite software package that implements this methodology and which may provide the means for simpler interlaboratory comparisons and, perhaps most importantly, enable the rapid reduction of large quantities of data with maximum feedback to the user at each stage.
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.
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