Onset of the aerobic nitrogen cycle during the Great Oxidation Event

The rise of oxygen on the early Earth (about 2.4 billion years ago)1 caused a reorganization of marine nutrient cycles2, 3, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records4 lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales5 of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event)6. Our data fill a gap of about 400 million years in the temporal 15N/14N record4 and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton

Mineralogical and geochemical analysis of Fe-phases in drill-cores from the Triassic Stuttgart Formation at Ketzin CO₂ storage site before CO₂ arrival

Reactive iron (Fe) oxides and sheet silicate-bound Fe in reservoir rocks may affect the subsurface storage of CO2 through several processes by changing the capacity to buffer the acidification by CO2 and the permeability of the reservoir rock: (1) the reduction of three-valent Fe in anoxic environments can lead to an increase in pH, (2) under sulphidic conditions, Fe may drive sulphur cycling and lead to the formation of pyrite, and (3) the leaching of Fe from sheet silicates may affect silicate diagenesis. In order to evaluate the importance of Fe-reduction on the CO2 reservoir, we analysed the Fe geochemistry in drill-cores from the Triassic Stuttgart Formation (Schilfsandstein) recovered from the monitoring well at the CO2 test injection site near Ketzin, Germany. The reservoir rock is a porous, poorly to moderately cohesive fluvial sandstone containing up to 2–4 wt% reactive Fe. Based on a sequential extraction, most Fe falls into the dithionite-extractable Fe-fraction and Fe bound to sheet silicates, whereby some Fe in the dithionite-extractable Fe-fraction may have been leached from illite and smectite. Illite and smectite were detected in core samples by X-ray diffraction and confirmed as the main Fe-containing mineral phases by X-ray absorption spectroscopy. Chlorite is also present, but likely does not contribute much to the high amount of Fe in the silicate-bound fraction. The organic carbon content of the reservoir rock is extremely low (<0.3 wt%), thus likely limiting microbial Fe-reduction or sulphate reduction despite relatively high concentrations of reactive Fe-mineral phases in the reservoir rock and sulphate in the reservoir fluid. Both processes could, however, be fuelled by organic matter that is mobilized by the flow of supercritical CO2 or introduced with the drilling fluid. Over long time periods, a potential way of liberating additional reactive Fe could occur through weathering of silicates due to acidification by CO2

First Investigation of the Microbiology of the Deepest Layer of Ocean Crust

We would like to thank Frederick (Rick) Colwell for input on molecular analyses in low biomass environments, Donna Blackman, Benoît Ildefonse, Adélie Delacour, and Gretchen Früh-Green for discussions regarding geological and geochemical aspects of this manuscript, and the Integrated Ocean Drilling Program Expeditions 304/305 Science Party. We would also like to thank Captain Alex Simpson and the entire crew of the JOIDES Resolution.Conceived and designed the experiments: OUM MRF SJG. Performed the experiments: OUM TN MR JDVN AM. Analyzed the data: OUM TN MR JDVN AM. Contributed reagents/materials/analysis tools: TN MR JZ MRF SJG. Wrote the paper: OUM.The gabbroic layer comprises the majority of ocean crust. Opportunities to sample this expansive crustal environment are rare because of the technological demands of deep ocean drilling; thus, gabbroic microbial communities have not yet been studied. During the Integrated Ocean Drilling Program Expeditions 304 and 305, igneous rock samples were collected from 0.45-1391.01 meters below seafloor at Hole 1309D, located on the Atlantis Massif (30 °N, 42 °W). Microbial diversity in the rocks was analyzed by denaturing gradient gel electrophoresis and sequencing (Expedition 304), and terminal restriction fragment length polymorphism, cloning and sequencing, and functional gene microarray analysis (Expedition 305). The gabbroic microbial community was relatively depauperate, consisting of a low diversity of proteobacterial lineages closely related to Bacteria from hydrocarbon-dominated environments and to known hydrocarbon degraders, and there was little evidence of Archaea. Functional gene diversity in the gabbroic samples was analyzed with a microarray for metabolic genes (“GeoChip”), producing further evidence of genomic potential for hydrocarbon degradation - genes for aerobic methane and toluene oxidation. Genes coding for anaerobic respirations, such as nitrate reduction, sulfate reduction, and metal reduction, as well as genes for carbon fixation, nitrogen fixation, and ammonium-oxidation, were also present. Our results suggest that the gabbroic layer hosts a microbial community that can degrade hydrocarbons and fix carbon and nitrogen, and has the potential to employ a diversity of non-oxygen electron acceptors. This rare glimpse of the gabbroic ecosystem provides further support for the recent finding of hydrocarbons in deep ocean gabbro from Hole 1309D. It has been hypothesized that these hydrocarbons might originate abiotically from serpentinization reactions that are occurring deep in the Earth's crust, raising the possibility that the lithic microbial community reported here might utilize carbon sources produced independently of the surface biosphere.Yeshttp://www.plosone.org/static/editorial#pee

Data for: Nitrogen isotope evidence for stepwise oxygenation of the ocean during the Great Oxidation Event

Iron speciaton data in shales from the Turee Creek Formation, Western Australi

Data for: Nitrogen isotope evidence for stepwise oxygenation of the ocean during the Great Oxidation Event

Iron speciaton data in shales from the Turee Creek Formation, Western AustraliaTHIS DATASET IS ARCHIVED AT DANS/EASY, BUT NOT ACCESSIBLE HERE. TO VIEW A LIST OF FILES AND ACCESS THE FILES IN THIS DATASET CLICK ON THE DOI-LINK ABOV

Oxygen and nitrogen isotopes as tracers of fluid activities in serpentinites and metasediments during subduction

International audienceSummary N and O isotope systematics of a suite of high-pressure (HP) and ultrahigh-pressure (UHP) metasediments of the Schistes Lustrés nappe and metaperidotites of the Erro Tobbio Massif from the Alpine-Appennine system are compared with their unmetamorphosed or hydrothermally-altered equivalent from the same localities and from the South West Indian Ridge (SWIR). The HP and UHP rocks studied represent a sequence of pelagic sediments and altered ultramafic rocks subducted to different depths of down to 90 km along a cold geothermal gradient (8 °C/km). Unmetamorphosed and HP metasediments show the same range in δ15N values irrespective of their metamorphic grade and bulk nitrogen concentrations. Together with several other geochemical features (K, Rb and Cs contents, δD), this indicates that δ15N values were unaffected by metamorphism and N was not released during subduction. N isotope analysis of serpentinites coupled with δ18O systematics suggests the involvement of a mafic (crustal) component during partial deserpentinization of the subducted oceanic mantle at the depth locus of island arc magmatism. This does not imply large-scale fluxes as the metagabbros are spatially associated with the analyzed serpentinites. It rather indicates preservation of presubduction chemical and isotopic heterogeneities on a local scale as documented for the metasediments

Evidence for nitrogen enrichment during oceanic crust alteration

International audienc

Oxygen and nitrogen isotopes as tracers of fluid activities in serpentinites and metasediments during subduction

N and O isotope systematics of a suite of high-pressure (HP) and ultrahigh-pressure (UHP) metasediments of the Schistes Lustr\ue9s nappe and metaperidotites of the Erro Tobbio Massif from the Alpine-Appennine system are compared with their unmetamorphosed or hydrothermally-altered equivalent from the same localities and from the South West Indian Ridge (SWIR). The HP and UHP rocks studied represent a sequence of pelagic sediments and altered ultramafic rocks subducted to different depths of down to 90-km along a cold geothermal gradient (8 \ub0C/km). Unmetamorphosed and HP metasediments show the same range in \u3b415N values irrespective of their metamorphic grade and bulk nitrogen concentrations. Together with several other geochemical features (K, Rb and Cs contents, \u3b4D), this indicates that \u3b415N values were unaffected by metamorphism and N was not released during subduction. N isotope analysis of serpentinites coupled with \u3b418O systematics suggests the involvement of a mafic (crustal) component during partial deserpentinization of the subducted oceanic mantle at the depth locus of island arc magmatism. This does not imply large-scale fluxes as the metagabbros are spatially associated with the analyzed serpentinites. It rather indicates preservation of presubduction chemical and isotopic heterogeneities on a local scale as documented for the metasediments