High Spatial Resolution Isotopic Abundance Measurements by Secondary Ion Mass Spectrometry: Status and Prospects

Secondary Ion Mass Spectrometry, SIMS or ion microprobe analysis, has become an important tool for geochemistry because of its ability study the distributions of elemental and isotopic abundances in situ on polished samples with high (typically a few microns to sub-micron) spatial resolution. In addition, SIMS exhibits high sensitivity for a wide range of elements (H to Pu) so that isotope analyses can sometimes be performed for elements that comprise only trace quantities of some mineral phase (e.g., Pb in zircon) or on major and/or minor elements in very small samples (e.g., presolar dust grains). Offsetting these positive attributes are analytical difficulties due to the complexity of the sputtering source of analyte ions: (1) relatively efficient production of molecular ion species (especially from a complex matrix such as most natural minerals) that cause interferences at the same nominal mass as atomic ions of interest, and (2) quantitation problems caused by variations in the ionization efficiencies of different elements and/or isotopes depending upon the chemical state of the sample surface during sputtering--the so-called "matrix effects". Despite the availability of high mass resolution instruments (e.g., SHRIMP II/RG, CAMECA 1270/1280/NanoSIMS), the molecular ion interferences effectively limit the region of the mass table that can be investigated in most samples to isotope systems at Ni or lighter or at Os or heavier. The matrix effects and the sensitivity of instrumental mass discrimination to the physical state of the sample surface can hamper reproducibility and have contributed to a view that SIMS analyses, especially for so- called stable isotopes, are most appropriate for extraterrestrial samples which are often small, rare, and can exhibit large magnitude isotopic effects. Recent improvements in instrumentation and technique have extended the scope of SIMS isotopic analyses and applications now range from geochronology to paleoclimatology to volcanology to biogeochemistry and cosmochemistry. Multiple collector (static magnetic field) measurements at high mass resolving power have enabled high precision (sub-permil) for several stable isotopes systems (e.g., C, O, Mg, S). Applied to geochronology, the multiple collector approach permits very rapid survey of zircon Pb-Pb ages to identify candidate Hadean grains for further detailed analysis. Ion imaging has been used to correlate isotope compositions with biochemistry (e.g., FISH-SIMS) or to search for especially rare samples among larger populations (e.g., supernova grains of Stardust). For favorable sample geometries with lateral homogeneity, SIMS isotope analyses may be conducted in depth-profiling mode which brings spatial resolution into the tens of nm range. Applications of this approach include experimental petrology, thermochronology, and isotopic analyses of shallowly-implanted solar wind ions. New approaches to removal of molecular ion interferences include reverse- geometry instrumentation and accelerator-based SIMS. There always exists trade-offs between microanalysis and trace analysis on the one hand, and high precision on the other. In this contribution, I will review current status for isotope precision and accuracy of SIMS for applications in stable and radiogenic isotopes as a function of spatial scale. A discussion of current limits and future prospects for improvement in understanding matrix effects will be given. Examples from ion imaging/ depth profiling/ geochronology and cosmochemistry will be provided.