TITLE: Phosphorus recycling by mineral‑catalyzed ribonucleotide cleavage on iron and manganese oxides
—ABSTRACT: Phosphorus is an essential element influencing both food security via plant fertilization, and water pollution through excessive phosphorus use, yet the phosphorus cycle in ecosystems is poorly known. In particular, the abiotic dephosphorylation of biomolecules catalyzed by iron and manganese oxides is actually debated. Here, we studied the reaction of ribonucleotides with goethite, hematite, and birnessite both by mass spectrometry of solution species, and by molecular modeling simulations. Results disclose an up to fivefold preferential hydrolytic cleavage of a phosphoanhydride bond over a phosphoester bond, indicating that mineral-catalyzed reactions reflect the hierarchy reported for the phosphatase activity. The fourfold higher catalytic reactivity of goethite and birnessite versus hematite is explained by mineral-specific binding rather than surface area differences. Corresponding simulated adsorbate conformations at the water–mineral interfaces are proposed. Overall, our findings provide new insights on the catalytic recycling of organic phosphorus species by mineral oxides. [Link to Open Access Article]