Laboratory Simulation of an Iron(II)-rich Precambrian Marine Upwelling System to Explore the Growth of Photosynthetic Bacteria

A conventional concept for the deposition of some Precambrian Banded Iron Formations (BIF) proceeds on the assumption that ferrous iron [Fe(II)] upwelling from hydrothermal sources in the Precambrian ocean was oxidized by molecular oxygen [O2] produced by cyanobacteria. The oldest BIFs, deposited prior to the Great Oxidation Event (GOE) at about 2.4 billion years (Gy) ago, could have formed by direct oxidation of Fe(II) by anoxygenic photoferrotrophs under anoxic conditions. As a method for testing the geochemical and mineralogical patterns that develop under different biological scenarios, we designed a 40 cm long vertical flow-through column to simulate an anoxic Fe(II)-rich marine upwelling system representative of an ancient ocean on a lab scale. The cylinder was packed with a porous glass bead matrix to stabilize the geochemical gradients, and liquid samples for iron quantification could be taken throughout the water column. Dissolved oxygen was detected non-invasively via optodes from the outside. Results from biotic experiments that involved upwelling fluxes of Fe(II) from the bottom, a distinct light gradient from top, and cyanobacteria present in the water column, show clear evidence for the formation of Fe(III) mineral precipitates and development of a chemocline between Fe(II) and O2. This column allows us to test hypotheses for the formation of the BIFs by culturing cyanobacteria (and in the future photoferrotrophs) under simulated marine Precambrian conditions. Furthermore we hypothesize that our column concept allows for the simulation of various chemical and physical environments — including shallow marine or lacustrine sediments

Months-Long Spike in Aqueous Arsenic Following Domestic Well Installation and Disinfection: Short- and Long-Term Drinking Water Quality Implications

Exposure to high concentration geogenic arsenic via groundwater is a worldwide health concern. Well installation introduces oxic drilling fluids and hypochlorite (a strong oxidant) for disinfection, thus inducing geochemical disequilibrium. Well installation causes changes in geochemistry lasting 12 + months, as illustrated in a recent study of 250 new domestic wells in Minnesota, north-central United States. One study well had extremely high initial arsenic (1550 µg/L) that substantially decreased after 15 months (5.2 µg/L). The drilling and development of the study well were typical and ordinary; nothing observable indicated the very high initial arsenic concentration. We hypothesized that oxidation of arsenic-containing sulfides (which lowers pH) combined with low pH dissolution of arsenic-bearing Fe (oxyhydr)oxides caused the very high arsenic concentration. Geochemical equilibrium considerations and modeling supported our hypothesis. Groundwater equilibrium redox conditions are poised at the Fe(III)(s)/Fe(II)(aq) stability boundary, indicating arsenic-bearing Fe (oxyhydr)oxide mineral sensitivity to pH and redox changes. Changing groundwater geochemistry can have negative implications for home water treatment (e.g., reduced arsenic removal efficiency, iron fouling), which can lead to ongoing but unrecognized hazard of arsenic exposure from domestic well water. Our results may inform arsenic mobilization processes and geochemical sensitivity in similarly complex aquifers in Southeast Asia and elsewhere

Pervasively anoxic surface conditions at the onset of the Great Oxidation Event: new multi-proxy constraints from the Cooper Lake paleosol

Oceanic element inventories derived from marine sedimentary rocks place important constraints on oxidative continental weathering in deep time, but there remains a scarcity in complementary observations directly from continental sedimentary reservoirs. This study focuses on better defining continental weathering conditions near the Archean-Proterozoic boundary through the multi-proxy (major and ultra-trace element, Fe and Cr stable isotopes, μ-XRF elemental mapping, and detrital zircon U-Pb geochronology) investigation of the ca. 2.45 billion year old (giga annum, Ga) Cooper Lake paleosol (saprolith), developed on a sediment-hosted mafic dike within the Huronian Supergroup (Ontario, Canada). Throughout the variably altered Cooper Lake saprolith, ratios of immobile elements (Nb, Ta, Zr, Hf, Th, Al, Ti) are constant, indicating a uniform pre-alteration dike composition, lack of extreme pH weathering conditions, and no major influence from ligand-rich fluids during weathering or burial metasomatism/metamorphism. The loss of Mg, Fe, Na, Sr, and Li, a signature of albite and ferromagnesian silicate weathering, increases towards the top of the preserved profile (unconformity) and dike margins. Coupled bulk rock behaviour of Fe-Mg-Mn and co-localization of Fe- Mn in clay minerals (predominantly chlorite) indicates these elements were solubilized primarily in their divalent state without Fe/Mn-oxide formation. A lack of a Ce anomaly and immobility of Mo, V, and Cr further support pervasively anoxic weathering conditions. Subtle U enrichment is the only geochemical evidence, if primary, that could be consistent with oxidative element mobilization. The leaching of ferromagnesian silicates was accompanied by variable mobility and depletion of transition metals with a relative depletion order of Fe≈Mg≈Zn\u3eNi\u3eCo\u3eCu (Cu being significantly influenced by secondary sulfide formation). Mild enrichment of heavy Fe isotopes (δ56/54Fe from 0.169 to 0.492 ‰) correlating with Fe depletion in the saprolith indicates loss of isotopically light aqueous Fe(II). Minor REE+Y fractionation with increasing alteration intensity, including a decreasing Eu anomaly and Y/Ho ratio, is attributed to albite breakdown and preferential scavenging of HREE\u3eY by clay minerals, respectively. Younger metasomatism resulted in the addition of several elements (K, Rb, Cs, Be, Tl, Ba, Sn, In, W), partly or wholly obscuring their earlier paleo-weathering trends. The behavior of Cr at Cooper Lake can help test previous hypotheses of an enhanced, low pH-driven continental weathering flux of Cr(III) to marine reservoirs between ca. 2.48-2.32 Ga and the utility of the stable Cr isotope proxy of Mn-oxide induced Cr(III) oxidation. Synchrotron μ- XRF maps and invariant Cr/Nb ratios reveal complete immobility of Cr despite its distribution amongst both clay-rich groundmass and Fe-Ti oxides. Assuming a pH-dependent, continental source of Cr(III) to marine basins, the Cr immobility at Cooper Lake indicates either that signatures of acidic surface waters were localized to uppermost and typically unpreserved regolith horizons or were geographically restricted to acid-generating point sources. However, in given detrital pyrite preservation in fluvial sequences overlying the paleosol, we propose that the oxidative sulphide corrosion required to drive surface pH(δ53/52Cr: -0.321 ± 0.038 ‰, 2sd, n=34) that cannot be linked to Cr(III) oxidation and is instead interpreted to have a magmatic origin. The combined chemical signatures and continued preservation of detrital pyrite/uraninite indicate low atmospheric O2 during weathering at ca. 2.45 Ga preserved in the rift-related sedimentary rocks of the Lower Huronian. The aqueous flux from the reduced weathering of mafic rocks was characterized by a greater abundance of transition metals (Fe, Mn, Zn, Co, Ni) with isotopically light Fe(II), as well as higher Eu/Eu* and Y/Ho. In most models of Precambrian ocean element inventories, hydrothermal fluids are viewed as the main supplier of several metals (e.g., Fe, Zn), although the results herein suggest that a riverine metal supply may have been substantial and that using Eu-excess as a strict proxy for hydrothermal flux may be misleading in near-shore marine sedimentary environments

Microbially-mediated geochemical cycling of iron and nitrogen within the granite-hosted subsurface of Henderson Mine, CO

Microbial life unambiguously inhabits the deep, terrestrial subsurface. Although the nutrient and energy sources supporting deep life are largely unconstrained, they are likely to be geochemically–derived. Novel organisms and energy sources are consistently discovered in the subsurface, and expand the range of microbial diversity and biogeochemical processes encountered on Earth. This dissertation connects metabolisms predicted to support subsurface life inhabiting the fluids circulating through granite fractures and pore spaces in Henderson Mine, Colorado at a depth of 3000 feet to the specific microbes that are detected by culture-dependent and independent methods. The thermodynamics of potential inorganic redox reactions in Henderson fluids reveal that oxidation of metals (Fe, Mn), and reduced sulfur and nitrogen compounds with O2 can support microbes energetically, as can metabolisms utilizing nitrate, nitrite or metal-oxides as electron acceptors. Sulfate reduction is not favorable in Henderson fluids, in contrast to other deep mines where it is a dominant metabolism. Targeted culturing of chemolithoautotrophic microbes from Henderson resulted in the isolation of Ralstonia HM08–01 that grows by oxidizing Fe(II) with OO2 at circumneutral pH. This organism was abundant in 16S rRNA clone libraries of Henderson fluids, signifying that Fe–oxidation may support a significant proportion of biomass. The Fe–oxides produced in experiments were colloidal (50–100 nm diameter), persistent phases that would influence metal and nutrient transport if they form at Henderson. Aside from iron, ammonium (\u3e100 μM in borehole fluids) is an important energy source at Henderson. Nitrification is possibly mediated by Crenarchaea living in the Henderson fluids that possess the amoA gene for ammonia oxidation, and Nitrospira bacteria that possess the nxrB gene for nitrite oxidation. Although NH4+ substituted into K+–bearing minerals could theoretically supply subsurface microbes with geological ammonium, no ammonium was detected in Henderson minerals. Phylogenetic analysis of nifH genes for nitrogen fixation present at Henderson suggest the novel phylum of Henderson candidate division bacteria may be nitrogen fixers, and that ammonium is sourced biologically. These findings inform the reactions that are known to support subsurface life, the source of nutrients and energy sources for subsurface life, and the diversity of life that inhabits the subsurface

The biogeochemistry of ferruginous lakes and past ferruginous oceans

Anoxic and iron-rich (ferruginous) conditions prevailed in the ocean under the low-oxygen atmosphere that occurred through most of the Archean Eon. While euxinic conditions (i.e. anoxic and hydrogen sulfide-rich waters) became more common in the Proterozoic, ferruginous conditions persisted in deep waters. Ferruginous ocean regions would have been a major biosphere and Earth surface reservoir through which elements passed through as part of their global biogeochemical cycles. Understanding key biological events, such as the rise of oxygen in the atmosphere, or even the transitions from ferruginous to euxinic or oxic conditions, requires understanding the biogeochemical processes occurring within ferruginous oceans, and their indicators in the rock record. Important analogs for transitions between ferruginous and oxic or euxinic conditions are paleoferruginous lakes; their sediments commonly host siderite and Ca-carbonates, which are important Precambrian records of the carbon cycling. Lakes that were ferruginous in the past, or euxinic lakes with cryptic iron cycling may also help understand transitions between ferruginous and euxinic conditions in shallow and mid-depth oceanic waters during the Proterozoic. Modern ferruginous meromictic lakes, which host diverse anaerobic microbial communities, are increasingly utilized as biogeochemical analogues for ancient ferruginous oceans. Such lakes are believed to be rare, but regional and geological factors indicate they may be more common than previously thought. While physical mixing processes in lakes and oceans are notably different, many chemical and biological processes are similar. The diversity of sizes, stratifications, and water chemistries in ferruginous lakes thus can be leveraged to explore biogeochemical controls in a range of marine systems: near-shore, off-shore, silled basins, or those dominated by terrestrial or hydrothermal element sources. Ferruginous systems, both extant and extinct, lacustrine and marine, host a continuum of biogeochemical processes that highlight the important role of iron in the evolution of Earth’s surface environment

Physiology, Fe(II) oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

Evidence for Fe(II) oxidation and deposition of Fe(III)-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF). While the exact mechanisms of Fe(II) oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III) minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II)-rich) waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II) concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II) is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) are consistent with extracellular precipitation of Fe(III) (oxyhydr)oxide minerals, but that >10% of Fe(III) sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS) in Fe(II) toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II). These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life's greatest metabolic innovation, i.e., the evolution and activity of oxygenic photosynthesis, in ferruginous Precambrian oceans.This article is from Front. EarthSci.3:60. doi:10.3389/feart.2015.00060. Posted with permission.</p

Biological Fe(II) and As(III) Oxidation Immobilizes Arsenic in Micro-oxic Environments

Fe(III) oxyhydroxides play critical roles in arsenic immobilization due to their strong surface affinity for arsenic. However, the role of bacteria in Fe(II) oxidation and the subsequent immobilization of arsenic has not been thoroughly investigated to date, especially under the micro-oxic conditions present in soils and sediments where these microorganisms thrive. In the present study, we used gel-stabilized gradient systems to investigate arsenic immobilization during microaerophilic microbial Fe(II) oxidation and Fe(III) oxyhydroxide formation. The removal and immobilization of dissolved As(III) and As(V) proceeded via the formation of biogenic Fe(III) oxyhydroxides through microbial Fe(II) oxidation. After 30 days of incubation, the concentration of dissolved arsenic decreased from 600 to 4.8 μg L-1. When an Fe(III) oxyhydroxide formed in the presence of As(III), most of the arsenic ultimately was found as As(V), indicating that As(III) oxidation accompanied arsenic immobilization. The structure of the microbial community in As(III) incubations was highly differentiated with respect to the As(V)-bearing ending incubations. The As(III)-containing incubations contained the arsenite oxidase gene, suggesting the potential for microbially mediated As(III) oxidation. The findings of the present study suggest that As(III) immobilization can occur in micro-oxic environments after microbial Fe(II) oxidation and biogenic Fe(III) oxyhydroxide formation via the direct microbial oxidation of As(III) to As(V). This study demonstrates that microbial Fe(II) and As(III) oxidation are important geochemical processes for arsenic immobilization in micro-oxic soils and sediments

Microaerophilic Oxidation of Fe(II) Coupled with Simultaneous Carbon Fixation and As(III) Oxidation and Sequestration in Karstic Paddy Soil

Microaerophilic Fe(II)-oxidizing bacteria are often chemolithoautotrophs, and the Fe(III) (oxyhydr)oxides they form could immobilize arsenic (As). If such microbes are active in karstic paddy soils, their activity would help increase soil organic carbon and mitigate As contamination. We therefore used gel-stabilized gradient systems to cultivate microaerophilic Fe(II)-oxidizing bacteria from karstic paddy soil to investigate their capacity for Fe(II) oxidation, carbon fixation, and As sequestration. Stable isotope probing (SIP) demonstrated the assimilation of inorganic carbon at a maximum rate of 8.02 mmol C m-2 d-1. Sequencing revealed that Bradyrhizobium, Cupriavidus, Hyphomicrobium, Kaistobacter, Mesorhizobium, Rhizobium, unclassified Phycisphaerales, and unclassified Opitutaceas, were fixing carbon. Fe(II) oxidation produced Fe(III) (oxyhydr)oxides, which can absorb and/or co-precipitate As. Adding As(III) decreased the diversity of functional bacteria involved in carbon fixation, the relative abundance of predicted carbon fixation genes, and the amount of carbon fixed. Although the rate of Fe(II) oxidation was also lower in the presence of As(III), over 90% of the As(III) was sequestered after oxidation. The potential for microbially mediated As(III) oxidation was revealed by the presence of arsenite oxidase gene (aioA), denoting the potential of the Fe(II) oxidizing and autotrophic microbial community to also oxidize As(III). The results of this study demonstrate that carbon fixation coupled to Fe(II) oxidation can increase the carbon content in soils by microaerophilic Fe(II)-oxidizing bacteria, as well as accelerate As(III) oxidation and sequester it in association with Fe(III) (oxyhydr)oxides