Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (C_org) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ~1 cm, while SO₄²⁻ reduction accounted for the entire C_org oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of C_org oxidation rates. The relative contribution of Mn reduction to C_org oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 10⁵ cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm⁻³, while counts of Fe reducers were <10² cm⁻³. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ~10 μmol cm⁻³ and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche.     

Rates and regulation of microbial iron reduction in sediments of the Baltic-North Sea transition

The rates and pathways of anaerobic carbon mineralization processes were investigated at seven stations, ranging from 10 to 56 m water depth, in the Kattegat and Belt Sea, Denmark. Organic carbon mineralization coupled to microbial Mn and Fe reduction was quantified using anaerobic sediment incubation at two stations that were widely separated geographically within the study area. Fe reduction accounted for 75% of the anaerobic carbon oxidation at the station in the northern Kattegat, which is the highest percentage so far reported from subtidal marine sediment. By contrast, sulfate reduction was the dominant anaerobic respiration pathway (95%) at the station in the Great Belt. Dominance of Fe reduction was related to a relatively high sediment Fe content in combination with active reworking of the sediment by infauna. The relative contribution of Fe reduction to anaerobic carbon oxidation at both stations correlated with the concentration of poorly crystalline Fe(III), confirming that the concentration of poorly crystalline Fe(III) exerts a strong control on rates of Fe reduction in marine sediments. The dependence of microbial Fe reduction on concentrations of poorly crystalline Fe(III) was used to quantify the importance of Fe reduction at sites where anaerobic incubations were not applied. This study showed that Fe reduction is an important process in anaerobic carbon oxidation in a wider area of the seafloor in the northern and eastern Kattegat (contribution 60 – 75%). By contrast, Fe reduction is of little significance (6 – 25%) in the more coarse-grained sediments of the shallower western and southern Kattegat, where a low Fe content was an important limiting factor, and in fine-grained sediments of the Belt Sea (4 – 28%), where seasonal oxygen depletion limits the intensity of bioturbation and thereby the availability of Fe(III). A large fraction of the total deposition of organic matter in the Kattegat and Belt Sea occurs in the northern Kattegat, and we estimate 33% of benthic carbon oxidation in the whole area is conveyed by Fe reduction.     

Mycorrhiza and soil bacteria influence extractable iron and manganese in soil and uptake by soybean

Excess manganese (Mn) in soil is toxic to crops, but in some situations arbuscular mycorrhizal fungi (AMF) alleviate the toxic effects of Mn. Besides the increased phosphorus (P) uptake, mycorrhiza may affect the balance between Mn-reducing and Mn-oxidizing microorganisms in the mycorrhizosphere and affect the level of extractable Mn in soil. The aim of this work was to compare mycorrhizal and non-mycorrhizal plants that received extra P in relation to alleviation of Mn toxicity and the balance between Mn-oxidizing and Mn-reducing bacteria in the mycorrhizosphere. A clayey soil containing 508 mg kg⁻¹ of extractable Mn was fertilized with 30 mg kg⁻¹ (P1) or 45 mg kg⁻¹ (P2) of soluble P. Soybean (Glycine max L. Merrill, cv. IAC 8-2) plants at P1 level were non-inoculated (CP1) or inoculated with either Glomus etunicatum (GeP1) or G. macrocarpum (GmP1), while plants at P2 level were left non-inoculated (CP2). Plants were grown in a greenhouse and harvested after 80 days. In the mycorrhizosphere of the GmP1 and GeP1 plants a shift from Mn-oxidizing to Mn-reducing bacteria coincided with higher soil extractability of Mn and Fe. However, the occurrence of Mn-oxidizing/reducing bacteria in the (mycor)rhizosphere was unrelated to Mn toxicity in plants. Using 16S rDNA sequence homologies, the Mn-reducing isolates were consistent with the genus Streptomyces. The Mn-oxidizers were homologous with the genera Arthrobacter, Variovorax and Ralstonia. While CP1 plants showed Mn toxicity throughout the whole growth period, CP2 plants never did, in spite of having Fe and Mn shoot concentrations as high as in CP1 plants. Mycorrhizal plants showed Mn toxicity symptoms early in the growth period that were no longer visible in later growth stages. The shoot P concentration was almost twice as high in mycorrhizal plants compared with CP1 and CP2 plants. The shoot Mn and Fe concentrations and contents were lower in GmP1 and GeP1 plants compared with the CP2 treatment, even though levels of extractable metals increased in the soil when plants were mycorrhizal. This suggests that mycorrhiza protected its host plant from excessive uptake of Mn and Fe. In addition, higher tissue P concentrations may have facilitated internal detoxification of Mn in mycorrhizal plants. The exact mechanisms acting on alleviation of Mn toxicity in mycorrhizal plants should be further investigated.     

Oxide weathering and trace metal release by bacterial reduction in a New Caledonia Ferralsol

Bacterial reduction of Fe- and Mn-oxides was studied in a surfacehorizon of a New-Caledonian Ferralsol in batch experiments. Twotreatments were imposed containing different sources of organicmatter (soil organic matter with or without glucose addition) tolink organic matter biodegradation with reduction process. Theconcomitant solubilization of Ni and Co was also studied. Resultsshowed that anaerobic Fe- and Mn-reducing bacterial activity wasresponsible for Fe- and Mn-oxide solubilization by anaerobicrespiration or fermentation. When C was more available, oxidereduction was enhanced. Mn-oxide appeared as the major reduciblephase and metal source rather than goethite. Co and Ni weresolubilized with Fe and Mn but their amounts in solutiondecreased at the end of experiment. The bioavailability of heavymetals in this soil was increased by biological reduction but waslimited by adsorption or precipitation phenomena.     

A Hydrogen-Oxidizing, Fe(III)-Reducing Microorganism from the Great Bay Estuary, New Hampshire

A dissimilatory Fe(III)- and Mn(IV)-reducing bacterium was isolated from bottom sediments of the Great Bay estuary, New Hampshire. The isolate was a facultatively anaerobic gram-negative rod which did not appear to fit into any previously described genus. It was temporarily designated strain BrY. BrY grew anaerobically in a defined medium with hydrogen or lactate as the electron donor and Fe(III) as the electron acceptor. BrY required citrate, fumarate, or malate as a carbon source for growth on H₂ and Fe(III). With Fe(III) as the sole electron acceptor, BrY metabolized hydrogen to a minimum threshold at least 60-fold lower than the threshold reported for pure cultures of sulfate reducers. This finding supports the hypothesis that when Fe(III) is available, Fe(III) reducers can outcompete sulfate reducers for electron donors. Lactate was incompletely oxidized to acetate and carbon dioxide with Fe(III) as the electron acceptor. Lactate oxidation was also coupled to the reduction of Mn(IV), U(VI), fumarate, thiosulfate, or trimethylamine n-oxide under anaerobic conditions. BrY provides a model for how enzymatic metal reduction by respiratory metal-reducing microorganisms has the potential to contribute to the mobilization of iron and trace metals and to the immobilization of uranium in sediments of Great Bay Estuary.     

Hyperthermophilic Anaerobic Nitrate-Dependent Fe(II) Oxidization by Tibetan Hot Spring Microbiota and the Formation of Fe Minerals

Fe(II) in geothermal fluids was among the most important electron and energy sources for extremophiles and early life, and microbial oxidation of Fe(II) in turn contributed to the global Fe deposits such as banded iron formation (BIF). However, information was rare on Fe(II) bio-oxidation and consequent mineral formation in geothermal systems. In the present study, we investigated the anaerobic nitrate-depending Fe(II) oxidation (ANDFO) in the Tibetan hot springs with temperature ranging 52–86°C. ANDFO cultivation was established by inoculating sediments from the studied hot springs. Positive ANDFO reaction was observed in the cultures from three high-temperature hot springs (>80°C). Phylogenetic analysis showed that bacteria in the three obtained ANDFO cultures were mainly affiliated with phyla of Betaproteobacteria, Alphaproteobacteria, and Firmicutes. In the obtained ANDFO cultures, ferrous iron oxidation occurred with nitrate reduction, accompanied with the formation of magnetite and/or siderite, which could be finished within one week. The resulting euhedral magnetite was at the micrometer scale, which was larger in size and showed better crystallinity than its counterparts (usually <1?µm) formed by chemical reactions. Thus, it can be concluded that ANDFO bacteria and denitrifiers played important roles in the magnetite and siderite precipitation in the studied Tibetan hot springs. The coupling between Fe(II) oxidation and nitrate reduction mediated by thermophiles might provide a new mechanism for euhedral magnetite and siderite deposition in BIFs during the Precambrian period.     

Potentially Active Iron,Sulfur, and Sulfate Reducing Bacteria in Skagerrak and Bothnian Bay Sediments

In many marine surface sediments, the reduction of manganese (Mn) and iron (Fe) oxides is obscured by sulfate reduction, which is regarded as the predominant anaerobic microbial respiration process. However, many dissimilatory sulfate and sulfur reducing microorganisms are known to utilize alternative electron acceptors such as metal oxides. In this study, we tested whether sulfate and sulfur reducing bacteria are linked to metal oxide reduction based on biogeochemical modeling of porewater concentration profiles of Mn²⁺ and Fe²⁺ in Bothnian Bay (BB) and Skagerrak (SK) sediments. Steady-state modeling of Fe²⁺ and Mn²⁺ porewater profiles revealed zones of net Fe (0–9 cm BB; ～10 and 20 cm SK) and Mn (0–5 cm BB; 2–8 cm SK) species transformations. 16S rRNA pyrosequencing analysis of the in-situ community showed that Desulfobacteraceae, Desulfuromonadaceae and Desulfobulbaceae were present in the zone of Fe-reduction of both sediments. Rhodobacteraceae were also detected at high relative abundance in both sediments. BB sediments appeared to harbor a greater diversity of potential Fe-reducers compared to SK. Additionally, when the upper 10 cm of sediment from the SK was incubated with lepidocrocite and acetate, Desulfuromonas was the dominant bacteria. Real-time quantitative polymerase chain reaction (qPCR) results showed decreasing dsrA gene copy numbers with depth coincided with decreased Fe-reduction activity. Our results support the idea that sulfur and sulfate reducing bacteria contribute to Fe-reduction in the upper centimeters of both sediments.     

Manganese inhibition of microbial iron reduction in anaerobic sediments

Potential mechanisms for the lack of Fe(II) accumulation in Mn(IV)‐con‐taining anaerobic sediments were investigated. The addition of Mn(IV) to sediments in which Fe(III) reduction was the terminal electron‐accepting process removed all the pore‐water Fe(II), completely inhibited net Fe(III) reduction, and stimulated Mn(IV) reduction. In a solution buffered at pH 7, Mn(IV) oxidized Fe(II) to amorphic Fe(III) oxide. Mn(IV) naturally present in oxic freshwater sediments also rapidly oxidized Fe(II). A pure culture of a dissimilatory FE(III)‐ and Mn(FV)‐reducing organism isolated from the sediments reduced Fe(III) to Fe(II) in the presence of Mn(IV) when ferrozine was present to trap Fe(II) before Mn(IV) oxidized it. Depth profiles of dissolved iron and manganese reported in previous studies suggest that Fe(II) diffusing up from the zone of Fe(III) reduction is consumed within the Mn(IV)‐reducing zone. These results demonstrate that preferential reduction of Mn(IV) by Fe(III)‐reducing bacteria cannot completely explain the lack of Fe(II) accumulation in anaerobic, Mn(IV)‐containing sedments, and indicate that Mn(IV) oxidation of Fe(II) is the mechanism that ultimately prevents Fe(II) accumulation.     

Composition of Microbial Communities in Sediments from Southern Baikal Containing Fe/Mn Concretions

Massive parallel sequencing of the 16S rRNA gene fragments was used to investigate the composition and diversity of microbial communities in sediments from Southern Baikal to a depth of 9 cm with 1-cm step. In the layers from the sediment surface to the lower border of oxygen penetration (2 cm), organotrophic bacteria with high similarity to the heterotrophic species Luteolibacter luojiensis constituted the largest fraction of the community. In the formation zone of Fe/Mn crusts (3–5 cm), Proteobacteria and Actinobacteria predominated in the community, while the share of Cyanobacteria was considerable. The lower reduced layers showed an increased contribution of the Bacteroidetes, while the shares of the taxa predominant in the higher layers remained significant. Analysis of archaeal 16S rRNA gene amplicons revealed predominance of the soil and aquatic Thaumarchaeota (Marine Group I lineage), which are involved in anaerobic ammonium oxidation, practically in all sediment layers. The buried oxidized layer (6–7 cm), where members of the uncultured Marine Benthic Group D lineage of the order Thermoplasmatales (Euryarchaeota) predominated, was an exception in this regard. Small numbers of archaea of the Baikal-1 lineages (below 1%) were observed in the communities from the 6–7 and 7–8 cm layers, while the archaea involved in anaerobic methane oxidation (including the ANME-2d group) were not detected.     

Microbial metabolism of the carbon and sulfur cycles in Shira Lake (Khakasia)

Microbiological and biogeochemical studies of the meromictic saline Lake Shira (Khakasia) were conducted. In the upper part of the hydrogen-sulfide zone, at a depth of 13.5-14 m, there was a pale pink layer of water due to the development of purple bacteria (6 x 10(5) cells/ml), which were assigned by their morphological and spectral characteristics to Lamprocystis purpureus (formerly Amoebobacter purpurea). In August, the production of organic matter (OM) in Lake Shira was estimated to be 943 mg C/(m2 day). The contribution of anoxygenic photosynthesis was insignificant (about 7% of the total OM production). The share of bacterial chemosynthesis was still less (no more than 2%). In the anaerobic zone, the community of sulfate-reducing bacteria played a decisive role in the terminal decomposition of OM. The maximal rates of sulfate reduction were observed in the near-bottom water (114 micrograms S/(1 day)) and in the surface layer of bottom sediments (901 micrograms S/(dm3 day)). The daily expenditure of Corg for sulfate reduction was 73% of Corg formed daily in the processes of oxygenic and anoxygenic photosynthesis and bacterial chemosynthesis. The profile of methane distribution in the water column and bottom sediments was typical of meromictic reservoirs. The methane content in the water column increased beginning with the thermocline (7-8 m), and reached maximum values in the near-bottom water (17 microliters/l). In bottom sediments, the greatest methane concentrations (57 microliters/l) were observed in the surface layer (0-3 cm). The integral rate of methane formation in the water column and bottom sediments was almost an order of magnitude higher than the rate of its oxidation by aerobic and anaerobic methanotrophic microorganisms.     

Enrichment and characterization of marine anammox bacteria associated with global nitrogen gas production

Microbiological investigation of anaerobic ammonium oxidizing (anammox) bacteria has until now been restricted to wastewater species. The present study describes the enrichment and characterization of two marine Scalindua species, the anammox genus that dominates almost all natural habitats investigated so far. The species were enriched from a marine sediment in the Gullmar Fjord (Sweden) using a medium based on Red Sea salt. Anammox cells comprised about 90% of the enrichment culture after 10 months. The enriched Scalindua bacteria displayed all typical features known for anammox bacteria, including turnover of hydrazine, the presence of ladderane lipids, and a compartmentalized cellular ultrastructure. The Scalindua species also showed a nitrate-dependent use of formate, acetate and propionate, and performed a formate-dependent reduction of nitrate, Fe(III) and Mn(IV). This versatile metabolism may be the basis for the global distribution and substantial contribution of the marine Scalindua anammox bacteria to the nitrogen loss from oxygen-limited marine ecosystems.     

Dissimilatory Fe(III) and Mn(IV) reduction.

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.     

Isolation and characterization of a sulfur-oxidizing chemolithotroph growing on crude oil under anaerobic conditions

Molecular approaches have shown that a group of bacteria (called cluster 1 bacteria) affiliated with the epsilon subclass of the class Proteobacteria constituted major populations in underground crude-oil storage cavities. In order to unveil their physiology and ecological niche, this study isolated bacterial strains (exemplified by strain YK-1) affiliated with the cluster 1 bacteria from an oil storage cavity at Kuji in Iwate, Japan. 16S rRNA gene sequence analysis indicated that its closest relative was Thiomicrospira denitrificans (90% identity). Growth experiments under anaerobic conditions showed that strain YK-1 was a sulfur-oxidizing obligate chemolithotroph utilizing sulfide, elemental sulfur, thiosulfate, and hydrogen as electron donors and nitrate as an electron acceptor. Oxygen also supported its growth only under microaerobic conditions. Strain YK-1 could not grow on nitrite, and nitrite was the final product of nitrate reduction. Neither sugars, organic acids (including acetate), nor hydrocarbons could serve as carbon and energy sources. A typical stoichiometry of its energy metabolism followed an equation: S(2-) + 4NO(3)(-) --> SO(4)(2-) + 4NO(2)(-) (Delta G(0) = -534 kJ mol(-1)). In a difference from other anaerobic sulfur-oxidizing bacteria, this bacterium was sensitive to NaCl; growth in medium containing more than 1% NaCl was negligible. When YK-1 was grown anaerobically in a sulfur-depleted inorganic medium overlaid with crude oil, sulfate was produced, corresponding to its growth. On the contrary, YK-1 could not utilize crude oil as a carbon source. These results suggest that the cluster 1 bacteria yielded energy for growth in oil storage cavities by oxidizing petroleum sulfur compounds. Based on its physiology, ecological interactions with other members of the groundwater community are discussed.     

A new mechanism-based inhibitor of photosynthetic water oxidation: acetone hydrazone. 1. Equilibrium reactions

The process of photosynthetic water oxidation has been investigated by using a new type of water oxidation inhibitor, the alkyl hydrazones. Acetone hydrazone (AceH), (CH3)2CNNH2, inhibits water oxidation by a mechanism that is analogous to that of NH2OH. This involves binding to the water-oxidizing complex (WOC), followed by photoreversible reduction of manganese (loss of the S1----S2 reaction). At higher AceH concentrations the S1 state is reduced in the dark and Mn is released, albeit to a lesser extent than with NH2OH. Following extraction of Mn, AceH is able to donate electrons rapidly to the reaction center tyrosine radical Z+ (161Tyr-D1 protein), more slowly to a reaction center radical C+, and not at all to the dark-stable tyrosine radical D+ (160Tyr-D2 protein) which must be sequestered in an inaccessible site. Manganese, Z+, and C+ thus appear to be located in a common protein domain, with Mn being the first accessible donor, followed by Z+ and then C+. Photooxidation of Cyt b-559 is suppressed by AceH, indicating either reduction or competition for donation to P680+. Unexpectedly, Cl- was found not to interfere or compete with AceH for binding to the WOC in the S1 state, in contrast to the reported rate of binding of N,N-dimethylhydroxylamine, (CH3)2NOH [Beck, W., & Brudvig, G. (1988) J. Am. Chem. Soc. 110, 1517-1523]. We interpret the latter behavior as due to ionic screening of the thylakoid membrane, rather than a specific Cl- site involved in water oxidation.(ABSTRACT TRUNCATED AT 250 WORDS)     

Sublethal nickel toxicity shuts off manganese oxidation and pellicle biofilm formation in Pseudomonas putida GB-1

In sediments, the bioavailability and toxicity of Ni are strongly influenced by its sorption to manganese (Mn) oxides, which largely originate from the redox metabolism of microbes. However, microbes are concurrently susceptible to the toxic effects of Ni, which establishes complex interactions between toxicity and redox processes. This study measured the effect of Ni on growth, pellicle biofilm formation and oxidation of the Mn-oxidizing bacteria Pseudomonas putida GB-1. In liquid media, Ni exposure decreased the intrinsic growth rate but allowed growth to the stationary phase in all intermediate treatments. Manganese oxidation was 67% less than control for bacteria exposed to 5 μM Ni and completely ceased in all treatments above 50 μM. Pellicle biofilm development decreased exponentially with Ni concentration (maximum 92% reduction) and was replaced by planktonic growth in higher Ni treatments. In solid media assays, growth was unaffected by Ni exposure, but Mn oxidation completely ceased in treatments above 10 μM of Ni. Our results show that sublethal Ni concentrations substantially alter Mn oxidation rates and pellicle biofilm development in P. putida GB-1, which has implications for toxic metal bioavailability to the entire benthic community and the environmental consequences of metal contamination.     

Oxygen Dependency of Neutrophilic Fe(II) Oxidation by Leptothrix Differs from Abiotic Reaction

Neutrophilic Fe(II) oxidizing microorganisms are found in many natural environments. It has been hypothesized that, at low oxygen concentrations, microbial iron oxidation is favored over abiotic oxidation. Here, we compare the kinetics of abiotic Fe(II) oxidation to oxidation in the presence of the bacterium Leptothrix cholodnii Appels isolated from a wetland sediment. Rates of Fe(II) oxidation were determined in batch experiments at 20°C, pH 7 and oxygen concentrations between 3 and 120 μmol/l. The reaction progress in experiments with and without cells exhibited two distinct phases. During the initial phase, the oxygen dependency of microbial Fe(II) oxidation followed a Michaelis-Menten rate expression (K_M = 24.5 ± 10 μmol O₂/l, v_max = 1.8 ± 0.2 μmol Fe(II)/(l min) for 10⁸ cells/ml). In contrast, abiotic rates increased linearly with increasing oxygen concentrations. At similar oxygen concentrations, initial Fe(II) oxidation rates were faster in the experiments with bacteria. During the second phase, the accumulated iron oxides catalyzed further oxidative iron precipitation in both abiotic and microbial reaction systems. That is, abiotic oxidation also dominated the reaction progress in the presence of bacteria. In fact, in some experiments with bacteria, iron oxidation during the second phase proceeded slower than in the absence of bacteria, possibly due to an inhibitory effect of extracellular polymeric substances on the growth of Fe(III) oxides. Thus, our results suggest that the competitive advantage of microbial iron oxidation in low oxygen environments may be limited by the autocatalytic nature of abiotic Fe(III) oxide precipitation, unless the accumulation of Fe(III) oxides is prevented, for example, through a close coupling of Fe(II) oxidation and Fe(III) reduction.     

Reassessment of the Microbial Role in Mn-Fe Nodule Genesis in Andean Paleosols

The presence of Mn-Fe nodules in the epipedons (surface horizons) of paleosols of presumed Upper Neogene age in the northwestern Venezuelan Andes have been interpreted as products of inorganic oxidation and reduction processes operating over the full range of glacial and interglacial cycles that affected paleosol morphogenesis. New microscopic/chemical data from combined SEM-EDS-FIB analyses of representative Mn-Fe nodules indicate microbes play an important role in Mn/Fe precipitation leading to their genesis in alpine Mollisols (Argiustolls). Although the prevailing new data are based mainly on fossil forms of filamentous bacteria and fungi and other biogenic pseudomorphs that may represent the former resident bacteria, the presence of extant microbes must await field experiments/collection, followed by a molecular microbiology approach to determine the biological drivers of metal precipitation. As in other terrestrial niche environments, microbes are seen here to play a role, perhaps a key one, in the morphogenesis of paleosols of importance in upper Neogene paleoenvironmental reconstruction.     

In vitro studies indicate a quinone is involved in bacterial Mn(II) oxidation

Manganese(II)-oxidizing bacteria play an integral role in the cycling of Mn as well as other metals and organics. Prior work with Mn(II)-oxidizing bacteria suggested that Mn(II) oxidation involves a multicopper oxidase, but whether this enzyme directly catalyzes Mn(II) oxidation is unknown. For a clearer understanding of Mn(II) oxidation, we have undertaken biochemical studies in the model marine α-proteobacterium, Erythrobacter sp. strain SD21. The optimum pH for Mn(II)-oxidizing activity was 8.0 with a specific activity of 2.5 nmol × min⁻¹ × mg⁻¹ and a K _m = 204 μM. The activity was soluble suggesting a cytoplasmic or periplasmic protein. Mn(III) was an intermediate in the oxidation of Mn(II) and likely the primary product of enzymatic oxidation. The activity was stimulated by pyrroloquinoline quinone (PQQ), NAD⁺, and calcium but not by copper. In addition, PQQ rescued Pseudomonas putida MnB1 non Mn(II)-oxidizing mutants with insertions in the anthranilate synthase gene. The substrate and product of anthranilate synthase are intermediates in various quinone biosyntheses. Partially purified Mn(II) oxidase was enriched in quinones and had a UV/VIS absorption spectrum similar to a known quinone requiring enzyme but not to multicopper oxidases. These studies suggest that quinones may play an integral role in bacterial Mn(II) oxidation.     

Limited reduction of ferrihydrite encrusted by goethite in freshwater sediment

Many physical and chemical processes control the extent of Fe(III) oxyhydroxide reduction by dissimilatory Fe(III)‐reducing bacteria. The surface precipitation of secondary Fe minerals on Fe(III) oxyhydroxides limits the extent of microbial Fe(III) reduction, but this phenomenon has not yet been observed in nature. This paper reports the observation of secondary Fe‐mineral (goethite) encrustation on ferrihydrite surface within freshwater sediment up to 10 cm deep. The sediment surface was characterized by the predominance of ferrihydrites with biogenic stalks and sheaths. An Fe(II)‐oxidizing bacterium (Gallionellaceae) was detected by 16S rRNA gene analysis at sediment depths of 1 and 2 cm. Fe²⁺ concentration in the sediment pore water was relatively higher at 2–4 cm depths. The 16S rRNA genes affiliated with dissimilatory Fe(III)‐reducing bacteria were detected at 1, 2, and 4 cm depths. The results of the Fe K‐edge extended X‐ray absorption fine structure (EXAFS) analysis suggested the presence of goethite and siderite at depths below 3 cm. However, the change in the Fe‐mineral composition was restricted to sediment depths between 3 and 4 cm, despite the presence of abundant ferrihydrite at depths below 4 cm. An increase in CH₄ concentration was observed at deeper than 6 cm. Stable isotopic analysis of CH₄ in the pore water indicated that acetoclastic CH₄ occurred at depths below 7 cm. Transmission electron microscope observations suggested the presence of goethite and siderite on stalks and sheaths at depths below 3 cm. Results from conversion electron yield EXAFS analysis suggested that goethite dominated at 10 cm depth, thereby indicating that ferrihydrite was encrusted by goethite at this depth. Moreover, the incomplete reduction of ferrihydrite below depths of 4 cm was not due to the lack of organic carbon, but was possibly due to the surface encrustation of goethite on ferrihydrite.