Articles | Volume 14, issue 14
Biogeosciences, 14, 3585–3602, 2017
Biogeosciences, 14, 3585–3602, 2017

Research article 27 Jul 2017

Research article | 27 Jul 2017

Sediment phosphorus speciation and mobility under dynamic redox conditions

Chris T. Parsons1, Fereidoun Rezanezhad1, David W. O'Connell1,2, and Philippe Van Cappellen1 Chris T. Parsons et al.
  • 1Ecohydrology Research Group and The Water Institute, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, Canada
  • 2Department of Civil, Structural and Environmental Engineering, Trinity College Dublin, College Green, Museum Building, Dublin, Ireland

Abstract. Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ∼  2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h−1 kg−1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the activity of phosphomonoesterases was 37 % higher than under N2 sparging. The results emphasize that the magnitude and timing of internal P loading during periods of anoxia are dependent on both P redistribution within sediments and bottom-water nitrate concentrations.

Short summary
Phosphorus (P) has accumulated in sediments due to past human activities. The re-release of this P to water contributes to the growth of harmful algal blooms. Our research improves our mechanistic understanding of how P is partitioned between different chemical forms and between sediment and water under dynamic conditions. We demonstrate that P trapped within iron minerals may be less mobile during anoxic conditions than previously thought due to reversible changes to P forms within sediment.
Final-revised paper