Redox transition, surface sediment

Preliminary work (10) on the transition from oxidized surface sediment to reduced subsurface sediment in Milltown Reservoir showed that the redox transition occurs in the upper few tens of centimeters. Strong chemical gradients occur across this boundary. Ferrous iron in sediment pore water (groundwater and vadose water) is commonly below detection in the oxidizing surface zone and increases with depth. Arsenic is also low in pore water of the oxidized zone, but increases across the redox boundary, with As(III) as the dominant oxidation state in the reduced zone. Copper and zinc show the opposite trend, with relatively high concentrations in pore water of the oxidized surface sediment decreasing across the redox boundary. 

Redox Reactions. Aquatic organisms may alter the particular oxidation state of some elements in natural waters during activity. One of the most significant reactions of this type is sulfate reduction to sulfide in anoxic waters. The sulfide formed from this reaction can initiate several chemical reactions that can radically change the types and amounts of elements in solution. The classical example of this reaction is the reduction of ferric iron by sulfide. The resultant ferrous iron and other transition metals may precipitate with additional sulfide formed from further biochemically reduced sulfate. Iron reduction is often accompanied by a release of precipitated or sorbed phosphate. Gardner and Lee (21) and Lee (36) have shown that Lake Mendota surface sediments contain up to 20,000 p.p.m. of ferrous iron and a few thousand p.p.m. of sulfide. The biochemical formation of sulfide is undoubtedly important in determining the oxidation state and amounts of several elements in natural waters. 

The role of transition metal oxide/hydroxide minerals such as Fe and Mn oxides in redox reactions in soils and aqueous sediments is pronounced (Stumm and Morgan, 1980 Oscarson et al., 1981a). These oxides occur widely as suspended particles in surface waters and as coatings on soils and sediments (Taylor and McKenzie, 1966). 

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