Fe(III) Photoreduction Producing Fe_aq²⁺ in Oxic Freshwater Sediment

Iron(III) (Fe(III)) photoreduction plays an important role in Fe cycling and Fe(II) bioavailability in the upper ocean. Although well described for water columns, it is currently unknown to what extent light impacts the production of dissolved Fe(II) (Fe²⁺) in aquatic sediments. We performed high-resolution voltammetric microsensor measurements and demonstrated light-induced Fe²⁺ release in freshwater sediments from Lake Constance. Fe²⁺ concentrations increased up to 40 μM in the top 3 mm of the sediment during illumination in the visible range of light (400-700 nm), even in the presence of oxygen (100-280 μM). The Fe²⁺ release was strongly dependent on the organic matter content of the sediment. A lack of photoreduced Fe²⁺ was measured in sediments with concentrations of organic carbon <6 mg L^-1. The simultaneous presence of sedimentary Fe(III) photoreduction besides microbial and abiotic Fe²⁺ oxidation by oxygen suggests an active Fe redox cycling in the oxic and photic zone of aquatic sediments. Here, we provide evidence for a relevant contribution of Fe(III) photoreduction to the bio-geochemical Fe redox cycle in aquatic freshwater sediments.