Sedimentary Sulphur:Iron Ratio Indicates Vivianite Occurrence: A Study from Two Contrasting Freshwater Systems

PLoS One. 2015 Nov 24;10(11):e0143737. doi: 10.1371/journal.pone.0143737. eCollection 2015.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Fresh Water / chemistry*
  • Geologic Sediments / analysis*
  • Sulfur / analysis*
  • X-Ray Diffraction

Substances

  • Sulfur

Grants and funding

The study was funded by Deutsche Forschungsgemeinschaft (http://www.dfg.de/) within the project “RedoxPhos” (Grant Number: HU 740/5-1) (MH AK) and the framework programme Research for Sustainable Development (Grant Number: 033L041A) of the German Federal Ministry of Education and Research (http://www.bmbf.de/) within the research project NITROLIMIT (BG). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.