Eutrophication and global change are increasing the occurrence of seasonal hypoxia (bottom-water oxygen concentration <63 μM) in coastal systems worldwide. In extreme cases, the bottom water can become completely anoxic, allowing sulfide to escape from the sediments and leading to the development of bottom-water euxinia. In seasonally hypoxic coastal basins, electrogenic sulfur oxidation by long, filamentous cable bacteria has been shown to stimulate the formation of an iron oxide layer near the sediment-water interface, while the bottom waters are oxygenated. Upon the development of bottom-water anoxia, this iron oxide “firewall” prevents the sedimentary release of sulfide. Iron oxides also act as an adsorption trap for elements such as arsenic. Arsenic is a toxic trace metal, and its release from sediments can have a negative impact on marine ecosystems. Yet, it is currently unknown how electrogenic sulfur oxidation impacts arsenic cycling in seasonally hypoxic basins. In this study, we presented results from a seasonal field study of an uncontaminated marine lake, complemented with a long-term sediment core incubation experiment, which reveals that cable bacteria have a strong impact on the arsenic cycle in a seasonally hypoxic system. Electrogenic sulfur oxidation significantly modulates the arsenic fluxes over a seasonal time scale by enriching arsenic in the iron oxide layer near the sediment-water interface in the oxic period and pulse-releasing arsenic during the anoxic period. Fluxes as large as 20 μmol m⁻² day⁻¹ were measured, which are comparable to As fluxes reported from highly contaminated sediments. Since cable bacteria are recognized as active components of the microbial community in seasonally hypoxic systems worldwide, this seasonal amplification of arsenic fluxes is likely a widespread phenomenon.

The East Anglian salt marsh system (UK) has recently generated intriguing data with respect to sediment biogeochemistry. Neighbouring ponds in these salt marshes show two distinct regimes of redox cycling: the sediments are either iron-rich and bioturbated, or they are sulphide-rich and unbioturbated. No conclusive explanation has yet been given for this remarkable spatial co-occurrence. Here, we quantify the geochemical cycling in both pond types, using pore-water analyses and solid-phase speciation. Our results demonstrate that differences in solid-phase carbon and iron inputs are likely small between pond types, and so these cannot act as the direct driver of the observed redox dichotomy. Instead, our results suggest that the presence of bioturbation plays a key role in the transition from sulphur-dominated to iron-dominated sediments. The presence of burrowing fauna in marine sediments stimulates the mineralisation of organic matter, increases the iron cycling and limits the build-up of free sulphide. Overall, we propose that the observed dichotomy in pond geochemistry is due to alternative stable states, which result from non-linear interactions in the sedimentary iron and sulphur cycles that are amplified by bioturbation. This way, small differences in solid phase input can result in very different regimes of redox cycling due to positive feedbacks. This non-linearity in the iron and sulphur cycling could be an inherent feature of marine sediments, and hence, alternative stable states could be present in other systems.

Iron, manganese, and trace elements play an important role in the marine carbon cycle as they are limiting nutrients for marine primary productivity. Water column concentrations of these bio-essential elements are controlled by the balance between input and removal, with burial in marine sediments being the main sink. The efficiency of this burial sink is dependent on the redox state of the water column, with sediments underlying a sulphidic (euxinic) water column being the most efficient sinks for Fe, but also Mn and trace elements (Co, Cd, Ni, Mo, As, W, V, and U). Transient changes in ocean redox state can hence affect trace element burial, and correspondingly, the ocean's trace element inventory, but the impact of transient oxygenation events on trace element cycling is currently not well understood. Here, we investigate the impact of a natural oxygenation event on trace element release and burial in sediments of the Eastern Gotland Basin (EGB), a sub-basin of the Baltic Sea. After being anoxic (<0.5 µM O₂) for ∼10 years, the deep waters of the EGB experienced a natural oxygenation event (Major Baltic Inflow, MBI) in 2015. Following this oxygenation event, we deployed benthic chamber landers along a depth transect in the EGB in April 2016, 2017 and 2018. We complemented these in situ flux measurements with analyses of water column, solid phase and pore water chemistry. Overall, the event increased the benthic effluxes of dissolved trace elements, though particular responses were element-specific and were caused by different mechanisms. Enhanced fluxes of Cd and U were caused by oxidative remobilisation, while Ni showed little response to the inflow of oxygen. In contrast, enhanced release of Co, Mo, As, W, and V was caused by the enhanced transient input of Mn oxides into the sediment, whereas Fe oxides were of minor importance. Following the dissolution of the oxides in the sediment, Mn and W were nearly completely recycled back to the water column, while fractions of Fe, Co, Mo, As, and V were retained in the sediment. Our results suggest that transient oxygenation events in euxinic basins may decrease the water column inventory of certain trace elements (Fe, Co, Mo, As, and V), thus potentially affecting global marine primary productivity on longer timescales.