Beyond Equilibrium: Tracing Redox-Driven Pathways That Shape Aqueous and Mineral Chemistry

Abstract Numerous aqueous and geochemical systems host elements in multiple redox states, with wide ranging implications such as their influence on the formation/dissolution of minerals, water toxicity, and nutrient cycling. To uncover governing mechanisms and complex chemical interactions in geochemical systems, reactive-transport models have increasingly gained importance. However, their predictive capabilities remain limited because existing approaches struggle to accurately account for the full complexities of redox reactions. Here, we develop a reactive-transport framework that leverages recent advances in thermodynamic modeling, speciation chemistry, and redox kinetics. Distinct from traditional models, we uniquely treat redox kinetics along with transport as transient phenomena, decoupled from Gibbs free energy minimization. By ensuring ionic concentrations are governed by nonequilibrium rate laws, this approach allows predicting the tempo-spatial distribution of speciation and precipitation of species across oxidation states. We illustrate the versatility of our framework through two case studies: manganese speciation in natural waters and the fate of dissolved iron in aqueous/porous media. Our framework significantly enhances the modeling of a diverse range of redox-sensitive environments.