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Environmental context The cycling of iron plays an important role in pelagic boundary zones such as the oxic–anoxic interface where physical and chemical gradients occur. The turnover of iron in this zone depends on oxygen fluctuation and the duration of the fluctuation event. This study increases the understanding of biogeochemical iron transformation in such hotspots. Abstract In stratified iron-rich lakes, the interface between oxic and anoxic water bodies, the oxycline, is accompanied by a steep gradient of dissolved iron, the ferrocline. It is a hotspot of biogeochemical transformations, namely the cycling of iron (Fe). The rate of iron oxidation, both chemical and microbial, depends on pH, iron and oxygen concentration, and microbial activity. We investigated the ferrocline of the meromictic Lake Waldsee to find out how the ferrocline is influenced by fluctuating oxygen concentrations. We measured diurnal fluctuations of Fe2+, O2 and pH along vertical profiles during two campaigns in July and September 2011 as well as rates of iron oxidation in laboratory incubations. The oxygen content of the water column varied both between the campaigns and diurnally. We observed a diurnal intrusion of O2 into the ferrocline. The diurnal signal was visible in the iron profile in July but not in September. Iron oxidation rates determined in the laboratory demonstrate the importance of microbial iron reduction and the strong pH dependency. We related the reaction timescales for iron oxidation to the characteristic timescale of oxygen fluctuations by calculating non-dimensional numbers. This analysis showed that an oxygenation event had to last at least 10h in order to affect the depth and vertical extent of the ferrocline, which was the case in July but not in September. Our results show that the duration of events can be an important parameter regulating biogeochemical interactions in pelagic redoxclines.

Sediment diagenesis through microbial sulfate reduction is considered a critical process in the pH amelioration of acidic mine lakes, but is often limited by the availability of organic carbon. Organic substrates are therefore frequently added to mine lake sediments to stimulate sulfate reduction. Dissolved organic carbon (DOC) was added to sediment collected from three mine lakes, one (in Germany) with typically high concentrations of Fe and SO4 and another two (in Australia) with unusually low concentrations of Fe and SO4. After the DOC additions caused the dissolved oxygen concentrations in the overlying waters to fall below 50 μmol L–1, the sediment porewater at all sites progressed through the expected anaerobic respiration sequence. The paucity of Fe and SO4 in the Australian lakes did not appear to constrain microbial iron and sulfate reduction. Indeed, the low Fe concentrations appeared to promote microbial sulfate reduction in the Australian sites. In the German site, there was little evidence of sulfide production in the porewater and no changes in porewater pH profiles. In contrast, the sediment porewater from the two Australian sites exhibited sulfide production and increased porewater pH. Bioremediation of acidic lakes must consider the need to treat iron-rich water before attempting pH amelioration.