Direct Ion Speciation Analysis with Ion-Selective Membranes Operated in a Sequential Potentiometric/Time Resolved Chronopotentiometric Sensing Mode

Ion-selective membranes based on porous polypropylene membranes doped with an ionophore and a lipophilic cation-exchanger are used here in a new tandem measurement mode that combines dynamic electrochemistry and zero current potentiometry into a single protocol. Open circuit potential measurements yield near-Nernstian response slopes in complete analogy to established ion-selective electrode methodology. Such measurements are well established to give direct information on the so-called free ion concentration (strictly, activity) in the sample. The same membrane is here also operated in a constant current mode, in which the localized ion depletion at a transition time is visualized by chronopotentiometry. This dynamic electrochemistry methodology gives information on the labile ion concentration in the sample. The sequential protocol is established on potassium and calcium ion-selective membranes. An increase of the ionophore concentration in the membrane to 180 mM makes it possible to determine calcium concentrations as high as 3 mM by chronopotentiometry, thereby making it possible to directly detect total calcium in undiluted blood samples. Recovery times after current perturbation depend on the current amplitude but can be kept to below 1 min for the polypropylene based ion-selective membranes studied here. Plasticized PVC as membrane material is less suited for this protocol, especially when the measurement at elevated concentrations is desired. An analysis of current amplitudes, transition times, and concentrations shows that the data are described by the Sand equation and that migration effects are insignificant. A numerical model describes the experimental findings with good agreement and gives guidance on the required selectivity in order to observe a well-resolved transition time and on the expected errors due to insufficient selectivity. The simulations suggest that the methodology compares well to that of open circuit potentiometry, despite giving complementary information about the sample. The tandem methodology is demonstrated in a titration of calcium with nitrilotriacetic acid (NTA) and in the direct detection of calcium in undiluted heparinized and citrated blood.