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, beyond adsorption, the role of iron and manganese oxides in catalyzing the abiotic dephosphorylation of biomolecules is debated. Here, we studied the reactions of ribonucleotides, containing different phosphate bonding, with goethite, hematite, and birnessite. We employed both high-resolution mass spectrometry of solution species and molecular modeling simulations of ribonucleotide-mineral complexes. 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 activity of phosphatase enzymes. 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.

磷是一种重要元素，既通过植物施肥影响粮食安全，又通过过量磷使用影响水污染，但生态系统中的磷循环却鲜为人知。特别是，除了吸附之外，铁和锰氧化物在催化生物分子非生物去磷酸化中的作用也存在争议。在这里，我们研究了含有不同磷酸键的核糖核苷酸与针铁矿、赤铁矿和水钠铁矿的反应。我们采用了溶液种类的高分辨率质谱分析和核糖核苷酸-矿物质复合物的分子建模模拟。结果表明，磷酸酐键比磷酸酯键有高达五倍的优先水解裂解，表明矿物质催化反应反映了磷酸酶活性的报告层次。针铁矿和水钠锰矿的催化反应活性比赤铁矿高四倍，这是因为矿物特异性结合而不是表面积差异。提出了水-矿物质界面处相应的模拟吸附物构象。总的来说，我们的研究结果为矿物氧化物催化回收有机磷物质提供了新的见解。