Rethinking the biotic and abiotic remineralization of complex phosphate molecules in soils and sediments.

Phosphorus (P) is an essential macronutrient for all living organisms. Despite a diversity of P compounds in the environment, orthophosphate is the most bioavailable form of P. Remineralization of complex P molecules (e.g., organic P and phosphoanhydrides) into orthophosphate is traditionally considered to be carried out primarily by enzymes. Natural minerals are recently viewed to be abiotic catalysts (as compared to the organic phosphatases) to facilitate the cleavage of terminal P-O-C/P bonds and remineralization of complex P compounds. However, quantitative comparison between biotic and abiotic remineralization pathways of complex P molecules is still missing, impeding our capability to assess the importance and contribution of abiotic P remineralization in the environment. This study compares the hydrolysis rates of six organic phosphates and three inorganic phosphoanhydrides by representative enzymes (acid and alkaline phosphatases) and natural oxide minerals (hematite, birnessite, and boehmite). The results show that enzymes and minerals have different substrate preferences. Specifically, alkaline phosphatase hydrolyzes phosphate monoesters faster than phosphoanhydrides, whereas acid phosphatase and minerals show higher hydrolysis rates toward phosphoanhydrides than phosphate monoesters. Although the hydrolysis rates by enzymes (~µM hr-1) are orders of magnitude higher than those by minerals (~µM d-1), normalization of the rates by the natural abundance of enzymes and minerals leads to comparable contributions of both processes in soils and sediments. These results highlight the significance of natural minerals in the remineralization of complex P compounds, a process that was traditionally overlooked but with important implications for constraining P biogeochemical cycling in the environment.