Cable bacteria are long, filamentous bacteria with a unique metabolism involving centimetre-scale electron transport. They are widespread in the sediment of seasonally hypoxic systems and their metabolic activity stimulates the dissolution of iron sulfides (FeS), releasing large quantities of ferrous iron (Fe²⁺) into the pore water. Upon contact with oxygen, Fe²⁺ oxidation forms a layer of iron(oxyhydr)oxides (FeO_x), which in its turn can oxidize free sulfide (H₂S) and trap phosphorus (P) diffusing upward. The metabolism of cable bacteria could thus prevent the release of H₂S from the sediment and reduce the risk of euxinia, while at the same time modulating P release over seasonal timescales. However, experimental support for this so-called ‘iron firewall hypothesis’ is scarce. Here, we collected natural sediment in a seasonally hypoxic basin in three different seasons. Undisturbed sediment cores were incubated under anoxic conditions and the effluxes of H₂S, dissolved iron (dFe) and phosphate (PO₄³⁻) were monitored for up to 140 days. Cores with recent cable bacterial activity revealed a high stock of sedimentary FeO_x, which delayed the efflux of H₂S for up to 102 days. Our results demonstrate that the iron firewall mechanism could exert an important control on the prevalence of euxinia and regulate the P release in coastal oceans.

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.

It has been hypothesized that the evolution of animals during the Ediacaran-Cambrian transition stimulated the burial of phosphorus in marine sediments. This assumption is centrally based on data compilations from marine sediments deposited under oxic and anoxic bottom waters. Since anoxia excludes the presence of infauna and sediment reworking, the observed differences in P burial are assumed to be driven by the presence of bioturbators. This reasoning however ignores the potentially confounding impact of bottom-water oxygenation on phosphorus burial. Here, our goal is to test the idea that bioturbation increases the burial of organic and inorganic phosphorus (P<span classCombining double low line"inline-formula">org</span> and P<span classCombining double low line"inline-formula">inorg</span>, respectively) while accounting for bottom-water oxygenation. We present solid-phase phosphorus speciation data from salt marsh ponds with and without bioturbation (Blakeney salt marsh, Norfolk, UK). In both cases, the pond sediments are exposed to oxygenated bottom waters, and so the only difference is the presence or absence of bioturbating macrofauna. Our data reveal that the rate of P<span classCombining double low line"inline-formula">org</span> and P<span classCombining double low line"inline-formula">inorg</span> burial are indistinguishable between bioturbated and non-bioturbated sediments. A large terrestrial fraction of organic matter and higher sedimentation velocity than generally found in marine sediments (0.3 <span classCombining double low line"inline-formula">±</span> 0.1 cm yr<span classCombining double low line"inline-formula">-1</span>) may partially impact these results. However, the absence of a clear effect of bioturbation on total P burial puts into question the presumed importance of bioturbation for phosphorus burial.

For most of Earth's history, the ocean's interior was pervasively anoxic and showed occasional shifts in ocean redox chemistry between iron-buffered and sulfide-buffered states. These redox transitions are most often explained by large changes in external inputs, such as a strongly altered delivery of iron and sulfate to the ocean, or major shifts in marine productivity. Here, we propose that redox shifts can also arise from small perturbations that are amplified by nonlinear positive feedbacks within the internal iron and sulfur cycling of the ocean. Combining observational evidence with biogeochemical modeling, we show that both sedimentary and aquatic systems display intrinsic iron-sulfur bistability, which is tightly linked to the formation of reduced iron-sulfide minerals. The possibility of tipping points in the redox state of sediments and oceans, which allow large and nonreversible geochemical shifts to arise from relatively small changes in organic carbon input, has important implications for the interpretation of the geological rock record and the causes and consequences of major evolutionary transitions in the history of Earth's biosphere.

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.