New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

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 < 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.     

High‐Mg# Olivine,Clinopyroxene and Orthopyroxene Reference Materials for In Situ Oxygen Isotope Determination

Secondary ion mass spectrometry (SIMS) requires matrix‐matched reference materials to calibrate mass fractionation during oxygen isotope measurement. Over one thousand SIMS oxygen isotope measurements were conducted on eleven natural mineral samples (five olivines, three clinopyroxenes and three orthopyroxenes) in nineteen sessions using CAMECA IMS 1280 SIMS instruments to evaluate their potential as SIMS reference materials. The obtained results reveal oxygen isotope homogeneity of these samples. No matrix effect was measured for the same variety of mineral samples with limited Mg‐number variations (89.6–94.2, 90–91.9 and 90.1–92.1 for olivine, clinopyroxene and orthopyroxene, respectively). The recommended oxygen isotope compositions of these samples were determined using laser fluorination. These samples are therefore suitable to be used as reference materials for in situ oxygen isotope microanalysis.     

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.     

In Situ Determination of Au and Cu in Natural Pyrite by Near‐Infrared Femtosecond Laser Ablation‐Inductively Coupled Plasma‐Quadrupole Mass Spectrometry: No Evidence for Matrix Effects

Gold and copper concentrations were determined in natural pyrite by near‐infrared femtosecond LA‐ICP‐QMS, using both sulfide reference materials (pyrrhotite Po‐726 and in‐house natural chalcopyrite Cpy‐RM) and NIST SRM 610 as external calibrators. Firstly, using NIST SRM 610 as the external calibrator, we calculated the Au concentration in Po‐726 and the Cu concentration in Cpy‐RM. The calculated concentration averages for Au and Cu were similar to the values published for Po‐726 and Cpy‐RM, respectively. Secondly, we calculated Au and Cu concentrations taking NIST SRM 610 as an unknown sample and using Po‐726 and Cpy‐RM as external calibrators. Again, the average values obtained closely reflected the preferred concentrations for NIST SRM 610. Finally, we calculated Au and Cu concentrations in natural pyrite using sulfide and silicate reference materials as external calibrators. In both cases, calculated concentrations were very similar, independent of the external calibrator used. The aforementioned data, plus the fact that we obtained very small differences in relative sensitivity values (percentage differences are between 5% and 17% for ⁵⁷Fe, ⁶³Cu and ¹⁹⁷Au) on analyses of silicate and sulfide RMs, indicate that there were no matrix effects related to the differences in material composition. Thus, it is possible to determine Au and Cu in natural sulfides using NIST silicate glasses as an external calibrator.