Estimation of WHAM7 constants for GaIII, InIII, SbIII and BiIII from linear free energy relationships, and speciation calculations for natural waters

Abstract

Environmental contextNatural organic matter exerts a powerful control on chemical conditions in waters and soils, affecting pH and influencing the biological availability, transport and retention of metals. Modelling can help to predict these effects, but for many metals, model parameters are missing. We report parameters for four technology-critical elements in a chemical speciation model, and consider the chemistries of the elements in natural waters. AbstractWe compiled the equilibrium constants for the interactions of the technology-critical elements (TCEs) GaIII, InIII, SbIII and BiIII with ammonia, fluoride, hydroxyl and ligands with oxygen atoms. We then combined them with predictive equations to estimate parameters for Humic Ion-Binding Model VII, which permits the calculation of metal binding by natural organic matter (fulvic acid, FA, and humic acid, HA). Derived values of the Model VII parameter quantifying the interaction of metal ions with carboxyl-type groups (log KMA) were among the highest estimated so far, as were the values for the parameter (ΔLK2) that quantifies the tendency of the metal ion to interact with softer ligand atoms (N and S). The Windermere Humic Aqueous Model, version 7 (WHAM7), which incorporates Model VII, was then used to estimate the chemical speciation of each TCE element.