Sedimentary sulphur:iron ratio indicates vivianite occurrence: A study from two contrasting freshwater systems

Abstract

An increasing number of studies constrain the importance of iron for the long-term retention of phosphorus (P) under anoxic conditions, i.e. the formation of reduced iron phosphate minerals such as vivianite (Fe3(PO4)2·8H2O). Much remains unknown about vivianite formation, the factors controlling its occurrence, and its relevance for P burial during early sediment diagenesis. To study the occurrence of vivianite and to assess its relevance for P binding, surface sediments of two hydrologically contrasting waters were analysed by heavy-liquid separation and subsequent powder X-ray diffraction. In Lake Arendsee, vivianite was present in deeper sediment horizons and not in the uppermost layers with a sharp transition between vivianite and non-vivianite bearing layers. In contrast, in lowland river Lower Havel vivianite was present in the upper sediment layers and not in deeper horizons with a gradual transition between non-vivianite and vivianite bearing layers. In both waters, vivianite occurrence was accompanied by the presence of pyrite (FeS2). Vivianite formation was favoured by an elevated iron availability through a lower degree of sulphidisation and was present at a molar ratio of total sulphur to reactive iron smaller than 1.1, only. A longer lasting burden of sediments by organic matter, i.e. due to eutrophication, favours the release of sulphides, and the formation of insoluble iron sulphides leading to a lack of available iron and to less or no vivianite formation. This weakening in sedimentary P retention, representing a negative feedback mechanism (P release) in terms of water quality, could be partly compensated by harmless Fe amendments.