Iron oxides catalyze the hydrolysis of polyphosphate and precipitation of calcium phosphate minerals

Abstract

Interfacial chemistry of phosphorus (P) is important for understanding P sequestration and bioavailability in nature. Polyphosphate is a group of important P species in aquatic environments. The geochemical behaviors of polyphosphate at the mineral-water interface play critical roles in mediating aquatic P transformation, yet remain poorly constrained. This study investigates the hydrolysis of polyphosphate in the presence of four common iron (Fe) oxide minerals (ferrihydrite, hematite, goethite, lepidocrocite) and the subsequent precipitation of calcium phosphate minerals. Batch studies are combined with microscopic and spectroscopic characterizations to reveal P speciation and complexation state under varied solution chemistry (pH 6–9, 1 mM Ca2+, and artificial seawater). All four Fe oxides can hydrolyze polyphosphate and the hydrolysis rate and extent are both enhanced in the presence of Ca2+. In the presence of 1 mM Ca2+, the apparent hydrolysis rate fitted by first-order kinetic model follows the order of lepidocrocite > hematite > ferrihydrite > goethite. After normalization by specific surface area of Fe oxides, the hydrolysis rate is in the order of lepidocrocite ≈ goethite > hematite > ferrihydrite at pH 6, regardless of Ca2+ presence. At pH 7.5 and 9, the order of area-normalized apparent hydrolysis rate is lepidocrocite > goethite ≈ hematite > ferrihydrite. A terminal-only pathway via one-by-one cleavage of terminal phosphate groups is the dominant hydrolysis mechanism. Under alkaline conditions, amorphous calcium phosphate forms in the presence of Ca2+, which transforms to crystalline hydroxyapatite after long-term aging of 70 or 150 days. This study demonstrates the importance of natural minerals in controlling polyphosphate transformation into crystalline calcium phosphate minerals, and provides new insights for understanding P cycling and sequestration in the environment.