High-sensitivity tracing of stable isotope labeled Ag nanoparticles in environmental samples using MC-ICP-MS

Abstract

Silver nanoparticles (Ag NPs) are among the most widely used engineered nanomaterials and this warrants further investigation of their behaviour and fate in the environment. To support such work, we developed new techniques for efficient tracing of Ag NPs that are produced from, and hence labelled with, enriched ¹⁰⁹Ag (Ag-En). The methods encompass a one-step anion exchange separation of Ag from the sample matrix and precise determination of ¹⁰⁹Ag/¹⁰⁷Ag ratios and ¹⁰⁹Ag abundances by multiple-collector ICP-MS. The sample preparation procedure has an Ag yield of 104 ± 13% (1 SD) and a procedural Ag blank of less than 7 pg, enabling analysis of samples with only trace Ag contents. Analyses of Ag solutions and realistic samples show that careful correction of memory effects is paramount for ensuring data quality. Using appropriate procedures, the ¹⁰⁹Ag/¹⁰⁷Ag ratios of samples containing Ag-En can be determined to a precision and trueness of better than about 0.5%, when more than 0.5 ng Ag are available for analysis. Even if Ag is only present at 50 pg or less, the Ag isotope ratios and Ag-En concentrations of samples can be measured to better than 5 to 10%. The methods are therefore able to resolve the presence of 1 pg of Ag-En in samples that contain as little as 10 pg and to up to 1 ng of natural Ag. As such, the techniques allow robust detection and quantification of Ag-En in environmental samples even when highly variable quantities of Ag-En and natural Ag are present. The new methodology thus enables the use of stable isotope tracing to investigate the fate of Ag NPs in complex environmental systems at dosing concentrations similar to the predicted environmental concentrations and for very small samples, whilst also providing high sample throughput.