Analysis of nano-mineral chemistry with single particle ICP-Time-of-Flight-MS; a novel approach to discriminate between geological environments

Studies of indicator minerals and mineral chemistry are widely used in geochemistry and are particularly useful in mineral exploration. Due to the low abundance of indicator mineral grains, large field samples and extensive laboratory processing are required for these studies. However, nano- and submicron-scale mineral particles (NPs, diameter < 1 μm) are highly abundant in geochemical sample media, containing millions to billions of particles per gram of soil or sediment. In this study, we analyze mineral NPs using single particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOFMS), a recently developed technique for high throughput elemental characterization of NPs. We investigate the limitations of the technique that arise from the working range of the ICP-TOFMS instrument and the analytical uncertainty of measured element masses in single particles. Despite these limitations, spICP-TOFMS can be used to determine accurate element mass ratios in NPs, which we validated through analysis of mineral specimens. Elemental mass ratios obtained from spICP-TOFMS in the mineral specimens were supported by SEM-EDS. We analyzed the mineral chemistry of two pairs of elements, ZrHf and NbTa in geochemical samples (sediments, soils, and mine waste) adjacent to a carbonatite and a lithium‑cesium‑tantalum-type pegmatite. Hundreds to thousands of NPs were detected in only 30–80 min of spICP-TOFMS analysis, indicating that these particle types are highly abundant. Pegmatite-associated samples contained Hf and Ta-rich NPs, compared to carbonatite-associated samples that displayed the chondritic or crustal abundance mass ratios in single particles. Zr:Hf mass ratios measured in NPs by spICP-TOFMS were supported by LA-ICP-MS analysis of zircons from selected samples. Diagnostic nano-mineral compositions including Nb-Ta-Bi-Sb (large grains of which are rarely found) were abundant in pegmatite-associated samples, but virtually absent in carbonatite-associated samples. In this study, we demonstrate that the chemistry of mineral nanoparticles can be used to discriminate between geological environments, and for the first time, we show that spICP-TOFMS is an effective tool for this type of analysis.