Application of Isotopically Labeled Engineered Nanomaterials for Detection and Quantification in Soils via Single-Particle Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Finding and quantifying engineered nanomaterials (ENMs) in soil are challenging because of the abundance of natural nanomaterials (NNMs) with the same elemental composition, for example, TiO 2 . Isotopically enriched ENMs may be distinguished from NNMs with the same elemental composition using single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOF-MS) to measure multiple isotopes simultaneously within each ENM and NNM in soil, but the minimum isotope enrichment needed for detection of ENMs in soil is not known. Here, we determined the isotope enrichment needed for 47 Ti-enriched TiO 2 ENMs to be detectable in soil and assessed the effects of weathering on those requirements for less soluble TiO 2 and more soluble CuO ENMs. The isotope-enriched ENMs were dosed into two different soils and were extracted and measured by spICP-TOF-MS after 1, 7, and 30 days. Isotope-enriched ENMs were recovered and detected for all three time points. The 47 Ti-enriched TiO 2 ENMs were detectable in Lufa 2.2 soil at a nominal dosed concentration of 10 mg-TiO 2 kg -1 which is an environmentally relevant concentration in biosolid-amended soils. For distinguishing an ∼70 nm diameter TiO 2 ENM from TiO 2 NNMs in Lufa 2.2 soil, an ∼10 wt % 47 Ti isotope-enrichment was required, and this enrichment requirement increases as the particle size decreases. This study is the first to evaluate the tracking ability of isotope-enriched ENMs at an individual particle level in soil and provides guidance on the isotope enrichment requirements for quantification of ENMs made from Earth-abundant elements in soils.