Biogeochemical Cycling Of Iron Research Articles

A New Paradigm of Multiheme Cytochrome Evolution by Grafting and Pruning Protein Modules.

Multiheme cytochromes play key roles in diverse biogeochemical cycles, but understanding the origin and evolution of these proteins is a challenge due to their ancient origin and complex structure. Up until now, the evolution of multiheme cytochromes composed by multiple redox modules in a single polypeptide chain was proposed to occur by gene fusion events. In this context, the pentaheme nitrite reductase NrfA and the tetraheme cytochrome c554 were previously proposed to be at the origin of the extant octa- and nonaheme cytochrome c involved in metabolic pathways that contribute to the nitrogen, sulfur, and iron biogeochemical cycles by a gene fusion event. Here, we combine structural and character-based phylogenetic analysis with an unbiased root placement method to refine the evolutionary relationships between these multiheme cytochromes. The evidence show that NrfA and cytochrome c554 belong to different clades, which suggests that these two multiheme cytochromes are products of truncation of ancestral octaheme cytochromes related to extant octaheme nitrite reductase and MccA, respectively. From our phylogenetic analysis, the last common ancestor is predicted to be an octaheme cytochrome with nitrite reduction ability. Evolution from this octaheme framework led to the great diversity of extant multiheme cytochromes analyzed here by pruning and grafting of protein modules and hemes. By shedding light into the evolution of multiheme cytochromes that intervene in different biogeochemical cycles, this work contributes to our understanding about the interplay between biology and geochemistry across large time scales in the history of Earth.

Ferrozine colorimetry and reverse flow injection analysis (rFIA) based method for the determination of total iron in aqueous solutions at nanomolar concentrations

Iron is one of the most microbiologically and chemically important metals in natural waters. The biogeochemical cycling of iron is significantly influenced by the redox cycling of Fe(II) and Fe(III). Because of the unique chemistry of iron, it is often needed to analyze iron at nano-molar concentrations. This article describes a reverse flow injection analysis (rFIA) based method with ferrozine spectrophotometric detection to quantify total iron concentration in stream water at nanomolar concentrations. The rFIA system has a 0.65 nM detection limit and a linear dynamic range up to 1.40 μM for the total iron analysis. The detection limit was achieved using a 1.0 m long liquid waveguide capillary flow cell, 1.50 m long knotted reaction coil, 87.50 μL injection loop and a miniature fiber optics spectrophotometer. The optimized colorimetric reagent has 1.0 mM ferrozine, 0.1 M ascorbic acid, 1.0 mM citric acid and 0.10 M acetate buffer adjusted to pH 4.0. The best sample flow rate is 2.1 mL min−1 providing a sample throughput of more than 15 samples h−1. The linear dynamic range of the method can be adjusted by changing the volume of the injection loop. The rFIA manifold was assembled exclusively from commercially available components.

High molecular weight fractions of dissolved organic matter (DOM) determined the adsorption and electron transfer capacity of DOM on iron minerals

Dissolved organic matter (DOM) in the natural environment has a significant effect on the biogeochemical cycles of iron (Fe), such as adsorption and reduction reaction. However, the roles of the molecular weight (MW) fractions of DOM extracted from plants in adsorption onto Fe minerals coupled with the Fe reduction process are incompletely characterized. In this study, the effects of DOM (extracted from Carex cinerascens) with different MW fractions, labeled as low molecular DOM (L-DOM), medium molecular DOM (M-DOM), and high molecular DOM (H-DOM), respectively, on the adsorption onto Fe minerals and the electrons transfer capacity (ETC) during the Fe reduction process is investigated. The oxygen-rich and highly aromatic H-DOM exhibited stronger adsorption affinity onto Fe minerals, such as ferrihydrite, a poorly crystalline mineral, than other DOM fractions. The X-ray photoelectron spectra and the Fourier transform infrared spectra revealed that the functional groups of the oxygen-rich DOM, such as CO bonds and OCO bonds, preferentially adsorbed onto the Fe minerals. In addition, the cyclic voltammograms (CV) and the chronoamperometry (CA) measurements showed that H-DOM significantly enhanced the Fe reduction to its maximum extent, indicating that the efficiency of DOM on Fe reduction was strongly related to the ETC. Therefore, our findings confirm that H-DOM plays a key arole in the adsorption onto Fe minerals and Fe redox reaction. The results of this study may help evaluate the performance of the different MW of DOM from plants on the biogeochemical cycles of Fe in the soil environment.

Can the reductive dissolution of ferric iron in paddy soils compensate phosphorus limitation of rice plants and microorganisms?

Biogeochemical cycles of phosphorus (P) and iron (Fe) are tightly interlinked, especially in highly weathered acidic subtropical and tropical soils rich in iron (oxyhydr)oxides (Fe(III)). The quantitative contribution of the reductive dissolution of Fe(III)-bound inorganic P (Pi) (Fe–P) in low-redox paddy soils may cover the demands of rice plants (Oryza sativa L.) and microorganisms. We hypothesized that microbially-driven Fe(III) reduction and dissolution can cover the P demand of microorganisms but not of the young rice plants when the plants’ P demand is high but their root systems are not sufficiently developed. We grew pre-germinated rice plants for 33 days in flooded rhizoboxes filled with a paddy soil of low P availability. 32P-labeled ferrihydrite (30.8 mg kg−1) was supplied either (1) in polyamide mesh bags (30 μm mesh size) to prevent roots from directly mobilizing Fe–P (pellets-in-mesh bag treatment), or (2) in the same pellet form but without a mesh bag to enable roots accessing the Fe–P (pellets-no-mesh bag treatment).Without mesh bags, Pi was more available leading to increases in microbial biomass carbon (MBC) by 18–55% and nitrogen (MBN) by 4–108% in rooted soil as compared to Pi pellets not directly available to roots. The maximum enzyme activities (Vmax) of phosphomonoesterase and β-glucosidase followed this pattern. During rice root growth, day 10 to day 33, MBC and microbial biomass phosphorus (MBP) contents in both rooted and bottom bulk (15–18 cm) soil gradually decreased by 28–56% and 47–49%, respectively. In contrast to our hypothesis, the contribution of Fe–P to MBP remarkably decreased from 4.5% to almost zero from 10 to 33 days after rice transplantation, while Fe–P compensated up to 16% of the plant P uptake at 33 days after rice transplantation, thus outcompeting microorganisms. Although both plants and microorganisms obtained Pi released by Fe(III) reductive dissolution, this mechanism was not sufficient for the demand of either organism groups.

Microbial reduction and migration of As/Fe mediated by electron shuttle: Differences between incorporated and adsorbed As(V)

Metal-reducing bacteria play a central and important role in the biogeochemical cycle of arsenic (As) and iron (Fe). Research on As/Fe migration from arsenic-containing iron minerals mediated by electronic shuttles is of significance to groundwater protection and human health. Further, the redox activity and bioavailability of goethite with differing occurrence and distribution of arsenic have not been studied clearly. In this study, the function of electron shuttle AQDS in Fe(III) bioreduction was determined. It was found that acidic conditions were conducive to the growth and reproduction of strain D2201, which was beneficial to the reduction of As(V)/Fe(III). The OD600nm value of the bacteria at pH 6 exceeded twice that at pH 8. Then, three types of goethite, namely pure goethite (Gt), coprecipitated As(V)-goethite (Gt-As), and adsorbed arsenic-goethite (Gt∗As), were compared for microbial reduction reactivity. X-ray photoelectron spectroscopy analysis illustrated the proportion of OH- content in Gt-As was much lower than that of Gt and Gt∗As, indicating Gt-As carried more surface defects and had higher bioavailability. The Fe(II) content released from AQDS-mediated bioreduction of Gt-As was two-fold higher than that of Gt and Gt∗As at pH 7. In addition, pH significantly affected goethite bioreduction efficiency and arsenic migration degree. The dissolved Fe(II) concentration for Gt-As was 0.98, 0.133, and 0.139 ​mM at pH 6, 7, and 8, respectively; corresponding to dissolved As(T) content of 3.51, 1.48, and 1.31 ​μM within 9 days of culture. This study highlights the significant influence of AQDS and mineral structure on the As/Fe biochemical cycle, which will help further develop the bioremediation of arsenic-contaminated sediments.

Co-response of Fe-reducing/oxidizing bacteria and Fe species to the dynamic redox cycles of natural sediment

Fe(III)-reducing bacteria (FRB) and Fe(II)-oxidizing bacteria (FOB) play essential roles in the biogeochemical cycling of iron (Fe). Although the redox transformation of Fe species mediated by FRB/FOB has been extensively studied, the co-responses of FRB and FOB and Fe species transformation in natural sediment under dynamic redox conditions are poorly known. This study explored the variations of potential FRB and FOB abundances and Fe species transformation in natural sediment during successive anoxic-oxic-anoxic-oxic-anoxic cycles. Compared with the pristine sediment sample, the FRB abundance increased 121–793% (initial: (2.6 ± 0.6) × 107 copies/g) in the anoxic stages, while it decreased by 38–64% in the oxic stages. The increase in FRB abundance was ascribed to energy gain of FRB from the reduction of the amorphous Fe(III) (Fe(III)am) and the crystalline Fe(III) (Fe(III)cry) to the aqueous Fe(II) (Fe(II)aq), the adsorbed Fe(II) (Fe(II)ad) and the amorphous Fe(II) (Fe(II)am), while the decrease was attributed to the oxidative stress caused by the reactive oxidant produced from the abiotic oxidation of Fe(II)aq, Fe(II)ad and Fe(II)am to Fe(III)am and Fe(III)cry. The FOB abundance decreased 38–44% (initial: (5 ± 1.8) × 107 copies/g) in the second and third anoxic stages, while slightly fluctuated in the oxic periods. This observation was contrary to the variation of FRB, which might be attributed to the strong resistance to oxidative stress of FOB and its ability to obtain energy under oxic conditions. Although the functions of FRB and FOB were impaired during anoxic-oxic cycles, the transformation of Fe(II)/Fe(III) was not immediately affected, which may be related to the residual reactivity of dead bacteria and the bio-availability of Fe(II)/Fe(III) species. In the anoxic-oxic alternation process, the iron cycle is mainly the mutual transformation between Fe(II)aq, Fe(II)ad, Fe(II)am and Fe(III)am, Fe(III)cry. This finding deepens our understanding of the biogeochemical cycling of Fe in the redox-dynamic environments.

Redox-driven changes in organic C stabilization and Fe mineral transformations in temperate hydromorphic soils

Paddy soils experience long-term redox alternations affecting the interactions between the biogeochemical cycling of iron (Fe) and carbon (C). Differences in particle aggregation and soil organic matter (SOM) turnover are likely to both affect and be affected by the trajectory of Fe mineral evolution/crystallinity with redox fluctuations. We hypothesized that the legacy effects of redox cycling under paddy management affects particle aggregation, the distribution and mineralogy of Fe (hydr)oxides between particle-size fractions, and the interaction with SOM stabilization. Moreover, we expected underlying processes to be different in paddy eluvial and illuvial horizons, particularly due to the different inputs and redox conditions these horizons experience. To test these hypotheses, we evaluated the distribution of Fe species and organic C between different aggregate and particle-size fractions in topsoil (eluvial) and subsoil (illuvial) horizons of soils under long-term paddy and non-paddy management in NW Italy, as well as mineralogical changes in Fe phases by Fe K-edge Extended X-ray Adsorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopy. Our findings indicate that although paddy topsoils are depleted in hydrous Fe oxides with respect to non-paddy soils, they can stabilize important amounts of C through mineral associations, particularly with finer particle-size fractions rich in less crystalline Fe phases. We also show that redox cycling can influence microaggregate stability and consequently the distribution of Fe phases and OC between intra and inter-microaggregate fractions. On the other hand, illuvial horizons under paddy management were enriched in short-range ordered hydrous Fe oxides and this contributed to enhanced microaggregate formation and C stabilization with respect to non-paddy subsoils.

A coupled function of biochar as geobattery and geoconductor leads to stimulation of microbial Fe(III) reduction and methanogenesis in a paddy soil enrichment culture

Biochar can participate in biogeochemical electron transfer processes due to its electron-accepting and donating capabilities (i.e., geobattery) and electron conductivity (i.e., geoconductor). These two functions were separately demonstrated to play a role in biogeochemical iron cycling and methane formation. Yet, little is known about the coupled effect of both electron transfer mechanisms, even though naturally occurring electron transfer through biochar is expected to simultaneously rely on both geobattery and geoconductor mechanisms. Here, we incubated an anoxic paddy soil enrichment culture with acetate as the substrate to investigate how biochar's coupled electron transfer mechanisms influence the electron transfer pathways between microbes and Fe(III) minerals and how it impacts the soil microbial community composition. We found that biochar simultaneously stimulated microbial Fe(III) reduction and methanogenesis by 2.6 and 2.3 fold, but these processes were spatially decoupled. Small biochar particles (5–20 μm) caused higher Fe(III) reduction and methanogenesis rates than large particles (50–100 μm). The addition of biochar enriched a syntrophic acetate-oxidizing co-culture with dominating Fe(III)-reducing Geobacteraceae taxa and acetoclastic methanogenic Methanosarcina taxa. After acetoclastic methanogenesis stopped, the observed continuing methanogenesis was likely due to interspecies electron transfer caused by biochar functioning as a geoconductor transferring electrons from Geobacteraceae to Methanosarcina. In summary, the simultaneous occurrence of Fe(III) reduction and methanogenesis leads to the formation of a cell-biochar-mineral battery network and a cell-biochar-cell conductive network in an enrichment culture from a paddy soil.

Comment on “Biogeochemical cycling of iron (hydr-)oxides and its impact on organic carbon turnover in coastal wetlands: A global synthesis and perspective” [Earth-Science Reviews (2021) 103658

Models for a xenocryst origin for kimberlite olivines emphasise the similarity between their core compositions and those in mantle peridotites. While this permits a xenocryst origin, it does not provide proof, as magmas generated in equilibrium with mantle olivines could, in principle, crystallize initial olivines matching those in the source region. Further, in several kimberlites, there is a striking disparity between the compositional range of olivine cores and that in associated mantle peridotite xenoliths from the same locality. Olivine-liquid Mg-Fe exchange coefficients and Ni partition coefficients permit equilibrium between Mg-rich mantle olivines (Mg # ~ 94–93) and magmas matching kimberlite bulk rock compositions. Glass inclusions in olivine megacrysts from the Monastery kimberlite, with compositions which overlap the range of archetypal Group I kimberlites, were interpreted to represent original liquids trapped at pressures of 4.5–6 GPa. These glass inclusions provide direct petrographic support for primitive melts matching kimberlite bulk chemistry in the lower SCLM.A majority of kimberlitic olivines show normal (decreasing Mg #) core to rim zonation. Cores of normal-zoned kimberlitic olivines are typically homogeneous, but collectively define a field with a range in Mg # and invariant or slightly decreasing Ni towards more Fe-rich compositions. The most Mg-rich cores of normal-zoned olivines typically have Mg # in the range 94–93, but there are marked differences in the Fe-rich extreme of the normal-zoned population between different kimberlite clusters. Olivine rims typically define a field characterized by steeply decreasing Ni, coupled with invariant or slightly increasing or decreasing Mg #, which invariably overlaps the Fe-extreme of core compositions of the relatively Mg-rich, normal-zoned olivines. Consequently, while there is a sharp inflection in chemical gradient between the respective fields of cores and rims, they nevertheless define a continuous compositional field. Trace element modelling demonstrates that these zonation patterns can be explained in terms of a Raleigh crystallization model.Most, if not all kimberlites are characterized by a subordinate group of olivine macrocrysts with cores that are Fe-rich relative to the field for rims, and thus show reverse zonation, which are interpreted to be linked to the Cr-poor megacryst suite. Rare Mg-rich olivines (relative to rims), have high-pressure inclusions of garnet, clinopyroxene and orthopyroxene. When present, such inclusions often show disequilibrium features such as internal chemical zonation. This points to a very short mantle residence time prior to entrainment by the host kimberlite, indicating a link to the Cr-rich megacryst suite rather than mantle peridotites. In addition to a variable, but generally subordinate proportion of olivines derived from Cr-poor and Cr-rich megacrysts, xenocrysts derived from disaggregated mantle peridotites will undoubtedly be present. While their proportions are difficult to quantify, the collective evidence points to a cognate origin for a majority of kimberlitic olivines. A kimberlite magma ascent model is proposed which provides a framework for understanding both olivine compositional variation and apparently enigmatic internal and external olivine morphology.

Reply to comments by Thilo Rennert on “Biogeochemical cycling of iron (hydr-)oxides and its impact on organic carbon turnover in coastal wetlands: A global synthesis and perspective”. Earth-Science Reviews (2021) 103658

Phosphorus availability is considered a limiting factor in many scenarios for the origin of life. The concentration of P in environments of prebiotic interest will have been governed by the available mineral sources of P on the early Earth. A knowledge of early Earth P mineralogy and prevailing global and local environmental conditions is therefore needed to understand which scenarios for prebiotic chemistry are most plausible. Here, we review the plausible diversity of P-bearing phases at Earth's surface during the emergence of life. We consider phases that were delivered by meteorites (exogenous phases), as well as those that developed solely as a result of Earth system processes (endogenous phases). We take into account the known formation conditions of individual phases, as well as the observed temporal distributions of P-bearing minerals found at Earth's surface today. Our approach allows us to leverage what is known about changes in the Earth system in order to rule out the prebiotic relevance of many P-bearing phases. Meanwhile, we highlight a small number of phases that are of possible prebiotic relevance; specifically, exogenous schreibersite, merrillite, and apatite, and endogenous apatite, olivine, and glass. Prebiotic mineral-chemical scenarios can be formulated for each phase, with distinct requirements for the environmental and tectonic state of early Earth. We can therefore relate the plausibility of mineral-chemical scenarios to the nature of early Earth, bridging the fields of geoscience and prebiotic chemistry.

Metagenomic Insights Into the Microbial Iron Cycle of Subseafloor Habitats

Microbial iron cycling influences the flux of major nutrients in the environment (e.g., through the adsorptive capacity of iron oxides) and includes biotically induced iron oxidation and reduction processes. The ecological extent of microbial iron cycling is not well understood, even with increased sequencing efforts, in part due to limitations in gene annotation pipelines and limitations in experimental studies linking phenotype to genotype. This is particularly true for the marine subseafloor, which remains undersampled, but represents the largest contiguous habitat on Earth. To address this limitation, we used FeGenie, a database and bioinformatics tool that identifies microbial iron cycling genes and enables the development of testable hypotheses on the biogeochemical cycling of iron. Herein, we survey the microbial iron cycle in diverse subseafloor habitats, including sediment-buried crustal aquifers, as well as surficial and deep sediments. We inferred the genetic potential for iron redox cycling in 32 of the 46 metagenomes included in our analysis, demonstrating the prevalence of these activities across underexplored subseafloor ecosystems. We show that while some processes (e.g., iron uptake and storage, siderophore transport potential, and iron gene regulation) are near-universal, others (e.g., iron reduction/oxidation, siderophore synthesis, and magnetosome formation) are dependent on local redox and nutrient status. Additionally, we detected niche-specific differences in strategies used for dissimilatory iron reduction, suggesting that geochemical constraints likely play an important role in dictating the dominant mechanisms for iron cycling. Overall, our survey advances the known distribution, magnitude, and potential ecological impact of microbe-mediated iron cycling and utilization in sub-benthic ecosystems.

A Single Bacterium Capable of Oxidation and Reduction of Iron at Circumneutral pH.

ABSTRACTFe(II)-oxidizing microorganisms and Fe(III)-reducing microorganisms, which drive the biogeochemical Fe cycle on the Earth’s surface, are phylogenetically and ecologically diverse. However, no single organism capable of aerobic Fe(II) oxidation and anaerobic Fe(III) reduction at circumneutral pH have been reported so far. Here, we report a novel neutrophilic Fe(II)-oxidizing Rhodoferax bacterium, strain MIZ03, isolated from an iron-rich wetland in Japan. Our cultivation experiments demonstrate that MIZ03 represents a much more versatile metabolism for energy acquisition than previously recognized in the genus Rhodoferax. MIZ03 can grow chemolithoautotrophically at circumneutral pH by oxidation of Fe(II), H2, or thiosulfate as the sole electron donor under (micro)aerobic conditions (i.e., using O2 as the sole electron acceptor). In addition, it can reduce Fe(III) or nitrate under anaerobic conditions. Thus, this is the first report demonstrating the presence of a single bacterium capable of both Fe(II) oxidation and Fe(III) reduction at circumneutral pH. The observed physiology was consistent with its 4.9-Mbp complete genome encoding key genes for iron oxidation/reduction (foxEY and mtrABC), for nitrate reduction (narGHI), for thiosulfate oxidation (soxABCDXYZ), and for carbon fixation via the Calvin cycle. Our metagenomic survey suggests that there are more Rhodoferax members capable of Fe(II) oxidation and Fe(III) reduction. Such bifunctional Rhodoferax may have an ecological advantage in suboxic/anoxic environments at circumneutral pH by recycling of Fe as the electron donor and acceptor.IMPORTANCE The biogeochemical cycle of iron (Fe) via reactions of oxidation, reduction, precipitation, and dissolution is involved in the cycle of other ecologically relevant elements, such as C, N, P, S, As, Co, Ni, and Pb. The Fe cycle on the Earth’s surface is driven by a variety of Fe(II)-oxidizing microorganisms and Fe(III)-reducing microorganisms. Here, we discovered a novel bacterium, Rhodoferax sp. strain MIZ03, capable of both Fe(II) oxidation and Fe(III) reduction at circumneutral pH, and we report its physiological characteristics and complete genome sequence. The unexpected capability of this bacterium provides novel insights into the Fe cycle in the environment. Moreover, this bacterium will help to better understand the molecular mechanisms of microbial Fe redox cycling as a model organism.

Petrobactin, a siderophore produced by Alteromonas, mediates community iron acquisition in the global ocean

It is now widely accepted that siderophores play a role in marine iron biogeochemical cycling. However, the mechanisms by which siderophores affect the availability of iron from specific sources and the resulting significance of these processes on iron biogeochemical cycling as a whole have remained largely untested. In this study, we develop a model system for testing the effects of siderophore production on iron bioavailability using the marine copiotroph Alteromonas macleodii ATCC 27126. Through the generation of the knockout cell line ΔasbB::kmr, which lacks siderophore biosynthetic capabilities, we demonstrate that the production of the siderophore petrobactin enables the acquisition of iron from mineral sources and weaker iron-ligand complexes. Notably, the utilization of lithogenic iron, such as that from atmospheric dust, indicates a significant role for siderophores in the incorporation of new iron into marine systems. We have also detected petrobactin, a photoreactive siderophore, directly from seawater in the mid-latitudes of the North Pacific and have identified the biosynthetic pathway for petrobactin in bacterial metagenome-assembled genomes widely distributed across the global ocean. Together, these results improve our mechanistic understanding of the role of siderophore production in iron biogeochemical cycling in the marine environment wherein iron speciation, bioavailability, and residence time can be directly influenced by microbial activities.

Iron Cycle Tuned by Outer-Membrane Cytochromes of Dissimilatory Metal-Reducing Bacteria: Interfacial Dynamics and Mechanisms In Vitro.

The biogeochemical cycle of iron is of great importance to living organisms on Earth, and dissimilatory metal-reducing bacteria (DMRB) with the capability of reducing hematite (α-Fe2O3) by outer-membrane (OM) cytochromes play a great role in the iron cycle. However, the dynamic binding of cytochromes to α-Fe2O3 at the molecular level and the resulting impact on the photon-to-electron conversion of α-Fe2O3 for the iron cycle are not fully understood. To address these issues, two-dimensional IR correlation analysis coupled with molecular dynamics (MD) simulations was conducted for an OmcA-Fe2O3 system as OmcA bonds stronger with hematite in a typical DMRB,Shewanella. The photoelectric response of α-Fe2O3 with the OmcA coating was evaluated at three different potentials. Specifically, the binding groups from OmcA to α-Fe2O3 were in the sequence of carboxyl groups, amide II, and amide I. Further MD analysis reveals that both electrostatic interactions and hydrogen bonds played essential roles in the binding process, leading to the structural changes of OmcA to facilitate iron reduction. Moreover, the OmcA coating could store the photogenerated electrons from α-Fe2O3 like a capacitor and utilize the stored electrons for α-Fe2O3 reduction in dark and anoxic environments, further driving the biogeochemical cycle of iron. These investigations give the dynamic information on the OM protein/hematite interaction and provide fundamental insights into the biogeochemical cycle of iron by taking the photon-induced redox chemistry of iron oxide into consideration.

Enhanced sulfidization in a sedimentary turbidite layer from the Nansha Trough in the southern South China Sea

Microbial sulfate reduction occurs in diverse depositional sedimentary environments, especially in fine-grained sedimentary turbidites. However, the extent to which turbidites impact the mechanism of sulfidization and the carbon–sulfur–iron cycle is poorly understood. Here, a sediment gravity core (10GC) with 50-cm thick turbidites was collected from the Nansha Trough of the southwestern South China Sea (SSCS) to unravel the biogeochemistry and sulfidization processes. One accelerator mass spectrometric 14C date in the planktonic foraminifera indicates that the turbidite layer was deposited at or immediately before 16 ka. Using a suite of elemental (Fe, K, Si Al, and Zr) and sediment grain size proxies suggests that the sediments within the turbidites were derived from the Sunda Shelf and the Malay Peninsula. The TOC/TN values (9–20) of the turbidites indicate deposition of terrestrial organic matter with a mixture of C3 and C4 types of vegetation. The relatively negative 13CTIC values (−7.76‰ to 2.09‰) are robust evidence for the accumulation of authigenic carbonates, which was attributed to organoclastic sulfate reduction. The rather positive δ34SCRS (CRS: chromium reducible sulfur) (−37.5‰ to −10.5‰) and high CRS contents of the turbidites compared to the hemipelagic sediments suggest that the enhanced sulfidization occurred due to a high rate of sulfate reduction in the closed system. In contrast to the turbidites, the more negative δ34SCRS values (−50.9‰ to −47.4‰) in the hemipelagic sediments reflect early diagenetic pyritization at the sediment–water interface. This study highlights the importance of turbidite sedimentation on the biogeochemical cycling of sulfur, carbon, and iron. However, further research is needed to better understand and quantify the contribution of marine turbidite sediments to the global ocean C–S–Fe cycle.

Photoferrotrophy and phototrophic extracellular electron uptake is common in the marine anoxygenic phototroph Rhodovulum sulfidophilum.

Photoferrotrophy allows anoxygenic phototrophs to use reduced iron as an electron donor for primary productivity. Recent work shows that freshwater photoferrotrophs can use electrons from solid-phase conductive substances via phototrophic extracellular electron uptake (pEEU), and the two processes share the underlying electron uptake mechanism. However, the ability of marine phototrophs to perform photoferrotrophy and pEEU, and the contribution of these processes to primary productivity is largely unknown. To fill this knowledge gap, we isolated 15 new strains of the marine anoxygenic phototroph Rhodovulum sulfidophilum on electron donors such as acetate and thiosulfate. We observed that all of the R. sulfidophilum strains isolated can perform photoferrotrophy. We chose strain AB26 as a representative strain to study further, and find that it can also perform pEEU from poised electrodes. We show that during pEEU, AB26 transfers electrons to the photosynthetic electron transport chain. Furthermore, systems biology-guided mutant analysis shows that R. sulfidophilum AB26 uses a previously unknown diheme cytochrome c protein, which we call EeuP, for pEEU but not photoferrotrophy. Homologs of EeuP occur in a range of widely distributed marine microbes. Overall, these results suggest that photoferrotrophy and pEEU contribute to the biogeochemical cycling of iron and carbon in marine ecosystems.

Iron and sulfur cycling in the cGENIE.muffin Earth system model (v0.9.21)

Abstract. The coupled biogeochemical cycles of iron and sulfur are central to the long-term biogeochemical evolution of Earth's oceans. For instance, before the development of a persistently oxygenated deep ocean, the ocean interior likely alternated between states buffered by reduced sulfur (“euxinic”) and buffered by reduced iron (“ferruginous”), with important implications for the cycles and hence bioavailability of dissolved iron (and phosphate). Even after atmospheric oxygen concentrations rose to modern-like values, the ocean episodically continued to develop regions of euxinic or ferruginous conditions, such as those associated with past key intervals of organic carbon deposition (e.g. during the Cretaceous) and extinction events (e.g. at the Permian–Triassic boundary). A better understanding of the cycling of iron and sulfur in an anoxic ocean, how geochemical patterns in the ocean relate to the available spatially heterogeneous geological observations, and quantification of the feedback strengths between nutrient cycling, biological productivity, and ocean redox requires a spatially resolved representation of ocean circulation together with an extended set of (bio)geochemical reactions. Here, we extend the “muffin” release of the intermediate-complexity Earth system model cGENIE to now include an anoxic iron and sulfur cycle (expanding the existing oxic iron and sulfur cycles), enabling the model to simulate ferruginous and euxinic redox states as well as the precipitation of reduced iron and sulfur minerals (pyrite, siderite, greenalite) and attendant iron and sulfur isotope signatures, which we describe in full. Because tests against present-day (oxic) ocean iron cycling exercises only a small part of the new code, we use an idealized ocean configuration to explore model sensitivity across a selection of key parameters. We also present the spatial patterns of concentrations and δ56Fe and δ34S isotope signatures of both dissolved and solid-phase Fe and S species in an anoxic ocean as an example application. Our sensitivity analyses show that the first-order results of the model are relatively robust against the choice of kinetic parameter values within the Fe–S system and that simulated concentrations and reaction rates are comparable to those observed in process analogues for ancient oceans (i.e. anoxic lakes). Future model developments will address sedimentary recycling and benthic iron fluxes back to the water column, together with the coupling of nutrient (in particular phosphate) cycling to the iron cycle.

New insight into iron biogeochemical cycling in soil-rice plant system using iron isotope fractionation

Iron (Fe) migration in soil-plants is a critical part of Fe biogeochemical cycling in the earth surface system. Fe isotope fractionation analysis in the soil-rice system is promising for quantitatively assessing various pathways and clarifying Fe transformation processes. However, the mechanisms of Fe isotope fractionation in the soil-rice system are not well understood. In this study, the Fe isotopic compositions (δ56Fe) of rhizosphere soils, pore water, Fe plaque, and rice plant tissues at the jointing and mature stages of the plants were determined. The rice plants were slightly enriched in heavier δ56Fe by ∼0.3‰ relative to the soil, and the stele and cortex showed similar δ56Fe values, indicating that the uptake of Fe by rice plants predominantly occurred via Fe(III)-phytosiderophores (Fe(III)-PS) chelation, but not Fe(III) reduction. Additionally, at both the jointing and mature stages, the rice plant tissues showed similar δ56Fe values. However, the Fe isotope fractionation between the roots and stems (Δ56Feroot−stem) was 1.39 ± 0.13‰, which is similar to the previously Ab initio-calculated values between Fe(III)-citrate and Fe(III)- 2-deoxymugineic acid (DMA), indicating that both the phloem and xylem have similar δ56Fe values, and the major Fe-chelating substances in the phloem of the rice plants are Fe(III)-DMA and Fe(II)- Nicotianamine (NA). Therefore, this study demonstrates that Fe isotope fractionation can be used as a signature for interpreting the Fe uptake and translocation mechanism in the soil-rice system.

Isotopically “heavy” pyrite in marine sediments due to high sedimentation rates and non-steady-state deposition

AbstractSedimentary pyrite formation links the global biogeochemical cycles of carbon, sulfur, and iron, which, in turn, modulate the redox state of the planet's surficial environment over geological time scales. Accordingly, the sulfur isotopic composition (δ34S) of pyrite has been widely employed as a geochemical tool to probe the evolution of ocean chemistry. Characteristics of the depositional environment and post-depositional processes, however, can modify the δ34S signal that is captured in sedimentary pyrite and ultimately preserved in the geological record. Exploring sulfur and iron diagenesis within the Bornholm Basin, Baltic Sea, we find that higher sedimentation rates limit the near-surface sulfidization of reactive iron, facilitating its burial and hence the subsurface availability of reactive iron for continued and progressively more 34S-enriched sediment-hosted pyrite formation (δ34S ≈ −5‰). Using a diagenetic model, we show that the amount of pyrite formed at the sediment-water interface has increased over the past few centuries in response to expansion of water-column hypoxia, which also impacts the sulfur isotopic signature of pyrite at depth. This contribution highlights the critical role of reactive iron in pyrite formation and questions to what degree pyrite δ34S values truly reflect past global ocean chemistry and biogeochemical processes. This work strengthens our ability to extract local paleoenvironmental information from pyrite δ34S signatures.

An evolving view on biogeochemical cycling of iron.

Biogeochemical cycling of iron is crucial to many environmental processes, such as ocean productivity, carbon storage, greenhouse gas emissions and the fate of nutrients, toxic metals and metalloids. Knowledge of the underlying processes involved in iron cycling has accelerated in recent years along with appreciation of the complex network of biotic and abiotic reactions dictating the speciation, mobility and reactivity of iron in the environment. Recent studies have provided insights into novel processes in the biogeochemical iron cycle such as microbial ammonium oxidation and methane oxidation coupled to Fe(III) reduction. They have also revealed that processes in the biogeochemical iron cycle spatially overlap and may compete with each other, and that oxidation and reduction of iron occur cyclically or simultaneously in many environments. This Review discusses these advances with particular focus on their environmental consequences, including the formation of greenhouse gases and the fate of nutrients and contaminants.