Insights into Primary Ion Exchange between Ion-Selective Membranes and Solution. From Altering Natural Isotope Ratios to Isotope Dilution Inductively Coupled Plasma Mass Spectrometry Studies

[Image: see text] Although ion-selective electrodes have been routinely used for decades now, there are still gaps in experimental evidence regarding how these sensors operate. This especially applies to the exchange of primary ions occurring for systems already containing analyte ions from the pretreatment step. Herein, for the first time, we present an insight into this process looking at the effect of altered ratios of naturally occurring analyte isotopes and achieving isotopic equilibrium. Benefiting from the same chemical properties of all isotopes of analyte ions and spatial resolution offered by laser ablation and inductively coupled plasma mass spectrometry, obtaining insights into primary ion diffusion in the preconditioned membrane is possible. For systems that have reached isotopic equilibrium in the membrane through ion exchange and between the membrane phase and the sample, quantification of primary ions in the membrane is possible using an isotope dilution approach for a heterogeneous system (membrane–liquid sample). Experimental results obtained for silver-selective membrane show that the primary ion diffusion coefficient in the preconditioned membrane is close to (6 ± 1) × 10(–9) cm(2)/s, being somewhat lower compared to the previously reported values for other cations. Diffusion of ions in the membrane is the rate limiting step in achieving isotopic exchange equilibrium between the ion-selective membrane phase and sample solution. On the contrary to previous reports, quantification of silver present in the membrane clearly shows that contact of the membrane with silver nitrate solution of concentration 10(–3) M leads to pronounced accumulation of silver ions in the membrane, reaching almost 150% of ion exchanger amount. The magnitude of this effect increases for higher concentration of the electrolyte in the solution.