Redox Chemistry in the Root Zone of a Salt Marsh Sediment in the Tagus Estuary,Portugal

Measurements of O₂, Fe(II), Mn(II)and HS₅ in salt marshsediments in the Tagus Estuary, Portugal, made with a voltammetric microelectrode, reveal strong seasonal differences in pore water composition within the 20~cm deep root zone. In spring, oxygen was below detection limit except close to the sediment surface. Fe(II) was present below 5 cm in concentrations ranging from detection limit to 1700 M. In summer, oxygen was present in the pore water almost to the bottom of the root zone in concentrations ranging from detection limit to more than 100 M. The spatial variability was intense: O₂ concentrations as high as 78 M and as low as 25 M existed within 2~mm of each other. Fe(II) was below detection limit except towards the bottom of the root zone. In late fall, oxygen was found to 8 cm depth, but in concentrations lower than in summer, and Fe(II) was present below 9 cm. Mn(II) was found at levels declining from typical values of 200 M in spring to less than 20 M in late fall. With one exception, sulfide was below the detection limit in all measurements. During periods when dissolved Fe(II) is available in the pore water at the same time as ₂ is delivered by roots, iron-rich concretions can form on roots. These conditions, which lead to precipitation of iron oxide in the sediment adjacent to roots, exist in spring, when new roots infiltrate anoxic Fe(II) containing sediment. They do not exist in summer, when dissolved Fe(II) is unavailable, or in winter, when oxygen is unavailable. The seasonal redox pattern revealed by the pore water chemistry is driven by the annual cycle of growth and decay of roots.