Isotopic Imaging Using fsLA Single-Collector ICP-SFMS for Direct U/Th Dating of Small Archaeological Carbonates

We present a new methodology for the U/Th dating of carbonate materials using femtosecond laser ablation single-collector inductively coupled plasma sector field mass spectrometry (fsLA single-collector ICP-SFMS), isotopic mappings, and image processing. This approach allows working on samples at very low U levels (ng·g^-1). One of the major advantages of this imaging method is that it allows us to exploit deteriorated samples that could not be analyzed by conventional bulk U/Th dating methods, thanks to the identification of contaminated or leached areas at the scale of a few tens of microns and the subsequent correction for detrital ²³⁰Th incorporation. Only a few milligrams of material are required for measurement, which allows us to work on small samples such as shell fragments. The parameters of the fsLA single-collector ICP-SFMS coupling have been carefully optimized to ensure very high sensitivity detection and ultralow background while preserving good plasma robustness and a spatial resolution of 30 × 50 μm². The accuracy was evaluated from low-level U speleothems previously dated by a conventional U/Th dating technique involving digestion, resin purification, double spike, and detection by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). U/Th ages of two archaeological samples with U at low ng·g^-1 levels, a giant terrestrial snail shell and a burned ostrich eggshell, were determined. The measured U/Th ages are consistent with the expected ages determined by luminescence dating methods.