Ion-exchange technique (IET) for measuring Cu2+, Ni2+ and Zn2+ activities in soils contaminated with metal mixtures

Abstract

Environmental contextTerrestrial environments receiving trace metal contaminants are often impacted by more than one metal. This study demonstrates the adaptation of an ion-exchange technique to simultaneously obtain Cu2+, Ni2+ and Zn2+ activities in soil extracts. These measurements can be used to better understand and predict the behaviour and bioavailability of soil metals in metal–mixture contamination scenarios. AbstractReliable estimates of metal speciation are critical for predicting metal bioavailability and the toxicological effects of metal mixtures in the soil environment; however, simultaneous measurements of metal free ion activities in complex matrices pose a challenge. Although speciation models maybe useful, the uncertainty of metal binding to natural organic matter requires that such models be validated with empirical data. In this study, an ion-exchange resin technique (IET) was adapted for the analysis of Cu2+, Ni2+ and Zn2+ in soil extracts. The analysis was performed with three different soil types spiked with single and multiple metal additions to obtain a range of metal concentrations and combinations. Method detection limits of 0.006, 0.04 and 0.05µM for Cu2+, Ni2+ and Zn2+ were achieved. The values obtained by IET were comparable with those estimated by Visual MINTEQ, giving a root mean squared error of 0.21, 0.30 and 0.34 (n=30) for the Cu, Ni and Zn data. The Cu2+ activities obtained by IET were within an order of magnitude of those obtained by a Cu ion-selective electrode, being on average 6-fold greater, with better agreement occurring in samples having lower organic matter contents. The resulting soil metal speciation data revealed that the partitioning of soil Cu to the potentially bioavailable Cu2+ pool differed in the binary mixture with Ni compared with the single-metal Cu treatments. These data can be used to assess metal bioavailability and aid in the interpretation of ecotoxicological effects observed in soils where multiple metals are a concern.