RESUMO
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.
RESUMO
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 (FeOx), 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 (PO4 3-) were monitored for up to 140 days. Cores with recent cable bacterial activity revealed a high stock of sedimentary FeOx, 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.
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We developed a reaction-transport model capable of tracing iron isotopes in marine sediments to quantify the influence of bioturbation on the isotopic signature of the benthic dissolved (DFe) flux. By fitting the model to published data from marine sediments, we calibrated effective overall fractionation factors for iron reduction (-1.3), oxidation (+0.4), iron-sulfide precipitation (+0.5) and dissolution (-0.5) and pyrite precipitation (-0.7) that agree with literature values. Results show that for bottom-water oxygen concentrations greater than 50 µM, higher bioturbation increased the benthic DFe flux and its δ 56Fe signature. By contrast, for oxygen concentrations less than 50 µM, higher bioturbation decreased the benthic DFe flux and its δ 56Fe signature. The expressed overall fractionation of the benthic DFe flux relative to the δ 56Fe of the iron oxides entering the sediment ranges from -1.67 to 0.0. On a global scale, the presence of bioturbation increases sedimentary DFe release from approximately 70 G mol DFe yr-1 to approximately 160 G mol DFe yr-1 and decreases the δ 56Fe signature of the DFe flux.
RESUMO
The radiation of bioturbation during the Ediacaran-Cambrian transition has long been hypothesized to have oxygenated sediments, triggering an expansion of the habitable benthic zone and promoting increased infaunal tiering in early Paleozoic benthic communities. However, the effects of bioturbation on sediment oxygen are underexplored with respect to the importance of biomixing and bioirrigation, two bioturbation processes which can have opposite effects on sediment redox chemistry. We categorized trace fossils from the Ediacaran and Terreneuvian as biomixing or bioirrigation fossils and integrated sedimentological proxies for bioturbation intensity with biogeochemical modeling to simulate oxygen penetration depths through the Ediacaran-Cambrian transition. Ultimately, we find that despite dramatic increases in ichnodiversity in the Terreneuvian, biomixing remains the dominant bioturbation behavior, and in contrast to traditional assumptions, Ediacaran-Cambrian bioturbation was unlikely to have resulted in extensive oxygenation of shallow marine sediments globally.
Assuntos
Ecossistema , Oxirredução , Sedimentos Geológicos/química , FósseisRESUMO
Previous studies have demonstrated that e-SOx can regulate the sedimentary release of phosphorus (P) in brackish and marine sediments. When e-SOx is active, an iron (Fe) and manganese (Mn) oxide rich layer is formed near the sediment surface, which prevents P release. When e-SOx becomes inactive, the metal oxide layer is reduced via sulfide-mediated dissolution, and P is subsequently released to the water column. Cable bacteria have been shown to also occur in freshwater sediments. In these sediments, sulfide production is limited, and the metal oxide layer would thus dissolve less efficiently, leaving the P trapped at the sediment surface. This lack of an efficient dissolution mechanism implies that e-SOx could play an important role in the regulation of P availability in eutrophied freshwater streams. To test this hypothesis, we incubated sediments from a eutrophic freshwater river to investigate the impact of cable bacteria on sedimentary cycling of Fe, Mn and P. High-resolution depth profiling of pH, O2 and ΣH2S complemented with FISH analysis and high-throughput gene sequencing showed that the development of e-SOx activity was closely linked to the enrichment of cable bacteria in incubated sediments. Cable bacteria activity caused a strong acidification in the suboxic zone, leading to the dissolution of Fe and Mn minerals and consequently a strong release of dissolved Fe2+ and Mn2+ to the porewater. Oxidation of these mobilized ions at the sediment surface led to the formation of a metal oxide layer that trapped dissolved P, as shown by the enrichment of P-bearing metal oxides in the top layer of the sediment and low phosphate in the pore and overlying water. After e-SOx activity declined, the metal oxide layer did not dissolve and P remained trapped at the surface. Overall, our results suggested cable bacteria can play an important role to counteract eutrophication in freshwater systems.
Assuntos
Fósforo , Poluentes Químicos da Água , Sedimentos Geológicos/microbiologia , Água Doce/microbiologia , Óxidos , Água , Oxirredução , Bactérias , Sulfetos , Poluentes Químicos da Água/análiseRESUMO
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.
RESUMO
Cable bacteria (Deltaproteobacteria, Desulfobulbaceae) are long filamentous sulfur-oxidizing bacteria that generate long-distance electric currents running through the bacterial filaments. This way, they couple the oxidation of sulfide in deeper sediment layers to the reduction of oxygen or nitrate near the sediment-water interface. Cable bacteria are found in a wide range of aquatic sediments, but an accurate procedure to assess their abundance is lacking. We developed a qPCR approach that quantifies cable bacteria in relation to other bacteria within the family Desulfobulbaceae. Primer sets targeting cable bacteria, Desulfobulbaceae and the total bacterial community were applied in qPCR with DNA extracted from marine sediment incubations. Amplicon sequencing of the 16S rRNA gene V4 region confirmed that cable bacteria were accurately enumerated by qPCR, and suggested novel diversity of cable bacteria. The conjoint quantification of current densities and cell densities revealed that individual filaments carry a mean current of â¼110 pA and have a cell specific oxygen consumption rate of 69 fmol O2 cell-1 day-1. Overall, the qPCR method enables a better quantitative assessment of cable bacteria abundance, providing new metabolic insights at filament and cell level, and improving our understanding of the microbial ecology of electrogenic sediments.