Evaluation of laser ablation double-focusing SC-ICPMS for “common” lead isotopic measurements in silicate glasses and mineral

An analytical method for the in situ measurement of “common” Pb isotope ratios in silicate glasses and minerals using a 193-nm excimer laser ablation (LA) system with a double-focusing single-collector (SC)-ICPMS is presented and evaluated as a possible alternative to multiple-collector (MC)-ICPMS. This LA-SC-ICPMS technique employs fast-scanning ion deflectors to sequentially place a series of flat-topped isotope peaks into a single ion-counting detector at a fixed accelerating voltage and magnetic field strength. Reference materials (including NIST, MPI-DING, and USGS glasses) are used to identify two analytical artifacts on the Pb isotope ratios (expressed here as heavier/lighter isotopes) when corrected for mass bias relative to NIST SRM610. The first artifact is characterized by anomalously low Pb isotope ratios (~0.1%/AMU) when SRM610 is analyzed in raster mode as an unknown at small spot sizes (<25 µm), which may indicate that (1) SRM610 is isotopically heterogeneous on a small length scale and/or (2) there is a non-spectral matrix effect on the Pb isotope ratios related to differences in spot size. The second artifact is characterized by anomalously high Pb isotope ratios (<0.1%/AMU) for NIST SRM612 (in raster mode) and some Fe-rich glass reference materials (BCR-2G, GOR132-G, and T1-G). These offsets are thought to be caused by one or more non-spectral matrix effects related to differences in the ablation behavior, composition, or physical properties of these reference materials compared to the bracketing SRM610 standard. The precision (±2SD) of our LA-SC-ICPMS Pb isotopic measurements is similar to (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, or ^20XPb/²⁰⁶Pb) or better than (²⁰⁶Pb/²⁰⁴Pb,²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb, or ^20XPb/²⁰⁴Pb) a series of published studies that used a different type of SC-ICPMS and obtained a factor of ~3-4 higher sensitivity for Pb. An increase in the sensitivity of our LA-SC-ICPMS would likely improve the precision of the ^20XPb/²⁰⁶Pb and ^20XPb/^204Pb ratios for low-Pb materials (<5 ppm), possibly making the technique broadly similar to LA-MC-ICPMS (particularly compared to methods that rely upon at least one ion-counting detector). Further improvement in the precision of the ^20XPb/²⁰⁶Pb and ^20XPb/²⁰⁴Pb ratios for high-Pb materials (>5 ppm) by LA-SC-ICPMS is unlikely, and in this case, LA-MC-ICPMS remains the preferable analytical technique.