Evidence for vivianite formation and its contribution to long-term phosphorus retention in a recent lake sediment: a novel analytical approach

Vivianite, Fe-3 (PO4)(2)center dot 8H(2)O, is a ferrous iron phosphate mineral which forms in waterlogged soils and sediments. The phosphorus (P) bound in its crystal lattice is considered to be immobilised because vivianite is stable under anoxic, reducing, sedimentary conditions. Thus, vivianite formation can make a major contribution to P retention during early diagenesis. Much remains unknown about vivianite in sediments, because technical challenges have rendered direct identification and quantification difficult. To identify vivianite and assess its significance for P burial during early diagenesis we studied the consequences of a 1992/1993 in-lake application of FeCl3 and Fe(OH)(3) aimed at restoring Lake Gro beta-Glienicke (Berlin, Germany). In a novel approach, we firstly applied a heavy-liquid separation to the iron-rich surface sediments which allowed direct identification of vivianite by X-ray diffraction in the high-density (rho > 2.3 g cm(-3)) sediment fraction. Secondly, we assessed the contribution of vivianite to P retention, combining results from chemical digestion with magnetic susceptibility data derived from magnetic hysteresis measurements. Scanning electron microscopy revealed that the dark blue spherical vivianite nodules were 40-180 mu m in diameter, and formed of platy- and needle-shaped crystal aggregates. Although equilibrium calculations indicated supersaturation of vivianite throughout the upper 30 cm of the sediment, the vivianite deposits were homogeneously distributed within, and restricted to, the upper 23 cm only. Thus, supersaturated pore water alone can-not serve as a reliable predictor for the in situ formation of vivianite. In Lake Gro beta-Glienicke, vivianite formation continues to be triggered by the artificial iron amendment more than 20 yr ago, significantly contributing to P retention in surface sediments.