Dynamics of redox changes of iron caused by light-dark variations in littoral sediment of a freshwater lake

Depth profiles of oxygen concentration and the redox status of acid-extractable iron were measured in littoral sediment cores of Lake Constance incubated under a light–dark regimen of 12 h. While oxygen penetrated to 3.4±0.2 mm depth in the dark, photosynthetic oxygen production shifted the oxic–anoxic interface down to 4.0±0.2 mm or 5.9±1.6 mm depth, at low or high light intensity, respectively, and caused a net oxygen efflux into the water column. After a light–dark or dark–light transition, the oxygen concentration at the sediment surface reached a new steady state within about 20 min. The redox state of the bioavailable iron was determined in 1-mm slices of sediment subcores. After a dark period of 12 h, 85% of the acid-extractable iron (10.5 lmol cm 3 total) in the uppermost 8 mm was in the reduced state. Within 12 h at low or high light intensity, the proportion of ferrous iron decreased to 82 or 75%, respectively, corresponding to net rates of iron oxidation in the range of 244 and 732 nmol cm 3 h , respectively. About 55 or 82% of the iron oxidation at low or high light intensity occurred in the respective oxic zone of the sediment; the remaining part was oxidized in the anoxic zone, probably coupled to nitrate reduction. The areal rates of iron oxidation in the respective oxic layer (21 or 123 nmol cm 2 h 1 at low or high light intensity, respectively) would account for 4 and 23% of the total electron flow to oxygen, respectively. Light changes caused a rapid migration of the oxic–anoxic interface in the sediment, followed by a slow redox reaction of biologically available iron, thus providing temporal niches for aerobic iron oxidizers and anaerobic iron reducers.