Molecular Insights into the Synergistic Inhibition of Microplastics-Derived Dissolved Organic Matter and Anions on the Transformation of Ferrihydrite

Ferrihydrite (Fh), as a ubiquitous iron (oxyhydr)oxide, plays an essential role in nutrient cycling and pollutant transformation due to its high surface area and diversified reaction sites. In the natural environment, Fh transformation could be easily influenced by coexisting components (particularly dissolved organic matter (DOM) and anions). As a new and important carbon source, microplastic-derived DOM (MP-DOM) directly or indirectly affects the morphology and fate of Fh, but limited knowledge exists about the combined effect of MP-DOM and anions on Fh transformation. Herein, this study elucidates the joint effects of polystyrene DOM (PS-DOM) and anions (such as Cl^-, SO₄^2-, and PO₄^3-) on Fh transformation. Single anions (especially PO₄^3-) were shown to inhibit the transformation of Fh to hematite (Hm) by hindering the dissolution and recrystallization of Fe(III). However, the inhibitory effect was strongly enhanced when PS-DOM and anions coexisted, which is attributed to their synergetic effects on inhibiting dissolution/recrystallization by occupying more active sites and hindering electron transfer. Furthermore, Fh transformation was predominantly controlled by PS-DOM, especially those containing high-unsaturation, high-oxidation-state, and O-rich phenolic compounds. These findings provide a new perspective on the significance of considering the joint effects of DOM and anions in evaluating the transformation of iron minerals.