Role of manganese redox cycling for trace metals in the Baltic Sea

Abstract: Redox zones are defined by steep gradients of changing concentrations and changing redox potential. They form a transition zone between oxic and anoxic/sulfidic conditions, where nitrate, manganese and iron reduction occurs. These redox zones can be situated in the sediment as well as in the water column. In the Baltic Sea both types are found. In the Bothnian Bay, the northernmost part of the Baltic Sea, the water column is well oxygenated and the redox zone lies within the uppermost sediment (approximately 2 cm in extend). In the Baltic Proper several of the deeper basins are stratified with the redox zone hanging between 75 and 100 m in the water column reaching up to 20 m.The redox-sensitive trace metal manganese can be both electron donor and acceptor in redox zones depending on its oxidation state. Manganese is transformed between the dissolved Mn(II),(III) and the particulate Mn(III/IV). Hence, Mn plays an important role in trace metal cycling across redox zones in natural environments. Manganese particles serve as a carrier for adsorbed trace metals towards the anoxic/sulfidic zone in the water column and as a barrier in the sediment, which restricts dissolved trace elements from diffusing to the oxic zone.In this study water samples (dissolved fraction, <0.22 μm, and particulate fraction, >0.22 μm) from the pelagic redox zone in Landsort Deep, Baltic proper were analyzed. Furthermore, a sedimentary redox zone from the Bothnian Bay has been investigated. A Mn particle peak is detected within the pelagic redox zone at Landsort Deep. A strong correlation between these Mn particles and several oxyanions as Mo, V and W is observed. The oxyanions are adsorbed onto the freshly formed Mn particles in the redox zone, settle with the particles and are released when Mn particles are reduced to Mn2+ and dissolve. This mechanism can act as a pump for trace metals to the sulfidic zone, where the trace metals either can be enriched in the dissolved fraction or form sulfid particles.In the sediment Mn redox cycling leads to enrichment of trace metals in the top layer. The formation of a barrier of Mn-Fe hydroxides restricts trace metal exchange between bottom water and sediment. Freshening of the Bothnian Bay basin has led to an increased sequestering of trace metals in the uppermost sediment. Trace metal proxies show that primary production in the Bothnian Bay has decreased starting approximately 2500 years BP. That led to a shift in the deposition of sulfide forming elements mainly due to the lower input of reactive organic carbon from plankton and to the recent enrichment of elements together with Mn-Fe hydroxides.