Role of manganese oxides and oxyhydroxides in phosphate sequestration in natural aquatic environments

Abstract

Excessive inputs of phosphorus (P) to aquatic environments can lead to eutrophication. Adsorption of phosphate on Fe oxides is one of the main process that can limit P availability. Oxidized forms of Mn have also been suggested to play a role in P trapping. However, although a considerable number of studies have shown the relationships between the geochemistry of Fe and that of phosphates, few studies have attempted to show the direct links between Mn and P. In the present study, we studied the adsorption of phosphate on synthetized Mn(III) and Mn(IV) oxides placed under natural conditions. The aim was to compare the role of Fe and Mn oxides in phosphate adsorption. Two muddy sediments were collected in a river bed at the edge of a large agricultural area. A sandy sediment was collected downstream. A muddy and a sandy sample were taken in a coastal environment. The experiments on phosphate adsorption by sediment and Mn oxides were carried out in slurries containing in situ waters spiked with 10 μM phosphate. Control experiments without Mn-oxide addition showed that the natural sediments tested still had the capacity to adsorb phosphate, in particular due to the presence of reactive Fe(III) oxides, extractable by an ascorbate solution. The addition of Mn(III) and Mn(IV) oxides in much larger quantities than the initial quantity of Fe oxides had little impact on the rate of phosphate adsorption. For both Mn(III) and Mn(IV) oxides, the Mn/P ratio between added particulate Mn and adsorbed P was very high, with values between 260 and 1000. The Fe/P ratio of the iron oxides contained in the slurries was between 6 and 20. On average, the P adsorption capacity of the Fe oxides was 50 times greater than that of the Mn oxides. Manganese oxides are generally less abundant than iron oxides in natural environments. Mn oxides therefore play a minor role in P sequestration compared with Fe oxides. Even if there are environments where Mn oxides can concentrate, the reduction of Mn oxides and subsequent liberation of adsorbed P does not represent a major risk for eutrophication of aquatic ecosystems.