Diurnal shifts in co-distributions of sulfide and iron(II) and profiles of phosphate and ammonium in the rhizosphere of Zostera capricorni

High resolution, two dimensional distributions of porewater iron(II) and sulfide were measured, using colourimetric DET (diffusive equilibration in a thin film) and DGT (diffusive gradients in a thin film) techniques, respectively, in Zostera capricorni colonised sediments under both light and dark conditions. Low resolution depth profiles of ammonium and phosphate were measured using conventional DET and DGT methods, respectively. Porewater iron(II) and sulfide distributions showed a high degree of spatial heterogeneity under both light and dark conditions, and distributions were characterised by a complex mosaic of sediment zones dominated by either iron(II) or sulfide. However, there was a clear shift in overall redox conditions between light and dark conditions. During light deployments, iron(II) and sulfide concentrations were generally low throughout the rhizosphere, apart from a few distinct “hotspots” of high concentration. Whereas during dark deployments, high concentrations of iron(II) were sometimes measured in the near surface sediments and sulfide depth distributions migrated towards the sediment surface. Profiles of porewater ammonium and phosphate demonstrated an increase in ammonium concentrations under dark compared to light conditions. Surprisingly, despite the large changes in iron(II) distributions between light and dark conditions, phosphate profiles remained similar, indicating that adsorption/release of phosphate by iron(III) hydr(oxide) mineral formation and reduction was not a major factor regulating porewater phosphate concentrations in these sediments or that phosphate uptake by the seagrass roots persisted during the dark period. Overall, the results demonstrate that the photosynthetic activity of the seagrass played a significant role in regulating sulfide, iron(II) and ammonium concentrations in the rhizosphere, due to rates of radial oxygen loss and ammonium uptake by the roots and rhizomes being lower under dark compared to light conditions. This cyclic production and reduction of iron(III) hydr(oxides) in the rhizosphere may act as a buffering system preventing sulfide accumulation.