Determination of Background Concentrations of Ag, Pd, Pt and Au in Highly Mineralized Ground Waters at Sub-ng L–1 Concentrations by Online Matrix Separation/Pre-Concentration Coupled to ICP-SFMS

Though not regulated in directives such as the Water Framework Directive of the European Union, the investigation of geogenic background concentrations of certain elements such as precious metals is of increasing interest, in particular for the early detection of a potential environmental pollution due to the increased use in various industrial and technological applications and in medicine. However, the precise and accurate quantification of precious metals in natural waters is challenging due to the complex matrices and the ultra-low concentrations in the (sub-) ng L−1 range. A methodological approach, based on matrix separation and pre-concentration on the strong anion exchange resin TEVA® Resin in an online mode directly coupled to ICP-SFMS, has been developed for the determination of Ag, Pt, Pd and Au in ground water. Membrane desolvation sample introduction was used to reduce oxide-based spectral interferences, which complicate the quantification of these metals with high accuracy. To overcome errors arising from matrix effects—in particular, the highly varying major ion composition of the investigated ground water samples—an isotope dilution analysis and quantification based on standard additions, respectively, were performed. The method allowed to process four samples per hour in a fully automated mode. With a sample volume of only 8 mL, enrichment factors of 6–9 could be achieved, yielding detection limits <1 ng L−1. Validation of the trueness was performed based on the reference samples. This method has been used for the analysis of the total concentrations of Ag, Pt, Pd and Au in highly mineralized ground waters collected from springs located in important geological fault zones of Austria’s territory. Concentrations ranges of 0.21–64.2 ng L−1 for Ag, 0.65–6.26 ng L−1 for Pd, 0.07–1.55 ng L−1 for Pt and 0.26–1.95 ng L−1 for Au were found.