Environmental context Acidification of inland waterways is an emerging issue worldwide, mostly because it disturbs the balance of reduced sulfur species in soils, sediments and mine tailings. We describe a pathway for wetland acidification through salt displacement and oxidation of Fe2+ from clay minerals. This alternative pathway for acidification raises environmental concerns because an increasing number of inland waterways are affected by increasing salinity. Abstract A wetland near the Murray River (south-eastern Australia) was found to have significant levels of exchangeable reduced iron (Fe2+) in the sediment clay-zone, and the potential for acidification under high salinity and oxidising conditions. Cation exchange experiments using purified clay from this site show relative affinities consistent with the lyotrophic series: Fe2+>Ca2+>Mg2+>H+>K+>Na+. This relative affinity is confirmed in Fe2+ displacement experiments using natural sediment clay. Proton production during oxidation of salt-treated sediments corresponds to that expected for the oxidation and hydrolysis of Fe2+ displaced from clay interlayers, taking into account the buffering properties of the sediment matrix. This work shows that wetland acidification can occur in low sulfur-containing wetlands and is not exclusively a problem associated with sulfidic sediments.
Studies on the sulfur-containing chelating agents. XLVI. Hydrolysis of thio-.BETA.-diketones and related amides in acetonitrile-water mixture.
