Iron reduction

In this study, three biological sand filter (BSF) were contaminated with a synthetic iron-[1500 mg L À1 Fe(II), 500 mg L À1 Fe(III)] and sulphate-rich (6000 mg L À1 SO 2À 4 ) acid mine drainage (AMD) (pH = 2), for 24 days, to assess the remediation capacity and the evolution of autochthonous bacterial communities (monitored by T-RFLP and 16S rRNA gene clone libraries). To stimulate BSF bioremediation involving sulphate-reducing bacteria, a readily degradable carbon source (glucose, 8000 mg L À1 ) was incorporated into the influent AMD. Complete neutralization and average removal efficiencies of 81.5 (AE5.6)%, 95.8 (AE1.2)% and 32.8 (AE14.0)% for Fe(II), Fe(III) and sulphate were observed, respectively. Our results suggest that microbial iron reduction and sulphate reduction associated with iron precipitation were the main processes contributing to AMD neutralization. The effect of AMD on BSF sediment bacterial communities was highly reproducible. There was a decrease in diversity, and notably a single dominant operational taxonomic unit (OTU), closely related to Clostridium beijerinckii, which represented up to 65% of the total community at the end of the study period.

Previous research investigating the speleogenesis of iron-ore caves (IOC) in the Quadrilátero Ferrífero, or "Iron Quadrangle," of Brazil suggests that microbial iron reduction and subsequent dissolution of the surrounding Fe(III) rich rocks is responsible for cave formation. A soft intra-wall substance (sub muros) containing iron-reducing bacteria (FeRB) was discovered underneath the durable crusts of cave walls. The goal of the study was to determine if reduction rates were comparable between sub muros samples, while additionally observing how different electron donors affect microbial iron reduction. To do this, I compared Fe(III) reduction rates between sub muros samples collected from two different caves, and additionally between three electron donors for bacterial growth: succinate, lactate and fructose. Batch incubations were conducted and Fe(II) production was monitored over 68 days. The obtained data suggest differences in reduction rates between sub muros samples, although this could be a result of differences in FeRB population or abundance. Use of different electron donors demonstrated various effects on iron reduction and dissolution, where higher rates of both were observed in the fructose-amended group. Further analysis is needed to determine the reason behind differing reduction rates, specifically monitoring of microbial communities present in the incubations over time.

Keywords: chal co py rite, ther mal treat ment, sul fur, sulfidation, X-ray dif frac tion phase ana lyse, cop per, leach ing, sul fu ric acid Ab stract The cop per leach ing from chal co py rite is rather com pli-cated pro cess due to its re frac tory na ture. There fore a big ef fort is paid to find more ef fec tive method for this pro cess. One pos si ble method is the ther mal treat ment of raw chal-co py rite ma te rial with sul fur. The cop per from prod ucts of ther mal sulfidation of chal co py rite con cen trate should be better leachable, while iron prod uct could be less leachable, what is an ad van tage. Ther mal sulfidation of the chal co py rite con cen trate was re al ized by heat ing of sam ples at tem per a tures of 300, 350 and 400 °C dur ing 1 hour at nor mal pres sure 0.1 MPa. The used amount of sul phur was 0, 0.5, 1, 2, 3 grams per 3 grams of con cen trate. More over, one sulfidation ex per i-ment was re al ized in evac u ated quartz tube. Achieved prod ucts wer...

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 Mn 2C and Fe 2C in Bothnian Bay (BB) and Skagerrak (SK) sediments. Steady-state modeling of Fe 2C and Mn 2C 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 Fereduction 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.

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Microbial activity is a potentially important yet poorly understood control on the fate and environmental impact of CO2 that leaks into aquifers from deep storage reservoirs. In this study we examine how variation in CO2 abundance affected competition between Fe(III) and SO4 2-reducers in anoxic bioreactors inoculated with a mixed-microbial community from a freshwater aquifer. We performed two sets of experiments: one with low CO2 partial pressure (~0.02 atm) in the headspace of the reactors and one with high CO2 partial pressure (~1 atm). A fluid residence time of 35 days was maintained in the reactors by replacing one-fifth of the aqueous volume with fresh medium every seven days. The aqueous medium was composed of groundwater amended with small amounts of acetate (250 µM), phosphate (1 µM), and ammonium (50 µM) to stimulate microbial activity. Synthetic goethite (1 mmol) and SO4 2-(500 µM influent concentration) were also available in each reactor to serve as electron acceptors. Results of this study show that higher CO2 abundance increased the ability of Fe(III) reducers to compete with SO4 2-reducers, leading to significant shifts in CO2 trapping and water quality. Mass-balance calculations and pyrosequencing results demonstrate that SO4 2-reducers were dominant in reactors with low CO2 content. They consumed 85% of the acetate after acetate consumption reached steady state while Fe(III) reducers consumed only 15% on average. In contrast, Fe(III) reducers were dominant during that same interval in reactors with high CO2 content, consuming at least 90% of the acetate while SO4 2reducers consumed a negligible amount (<1%). The higher rate of Fe(III) reduction in the high-CO2 bioreactors enhanced CO2 solubility trapping relative to the low-CO2 bioreactors by increasing alkalinity generation (6X). Hence, the shift in microbial activity we observed was a positive feedback on CO2 trapping. More rapid Fe(III) reduction degraded water quality, however, by leading to high Fe(II) concentration.

Bacterial assimilation reduction of iron in the treatment of non-metallics Natural non-metallics, including granitoide and quartz sands, often contain iron which decreases the whiteness of these raw materials. Insoluble Fe 3+ in these samples could be reduced to soluble Fe 2+ by bacteria of Bacillus spp. and Saccharomyces spp. The leaching effect, observed by the measurement of Fe 2+ concentration in a solution, showed higher activities of a bacterial kind isolated from the Bajkal lake and also by using of yeast Saccharomyces sp. during bioleaching of quartz sands. However, allkinds of Bacillus spp. isolated from the Slovak deposit and from Bajkal lake were very active in the iron reduction during bioleaching of the feldspar raw material. This metal was efficiently removed from quartz sands as documented by the Fe2O3 decrease (from 0,317 % to 0,126 %) and from feldpars raw materials by the Fe2O3 decrease (from 0,288 % to 0,115 %) after bioleaching. The whiteness of these non-metalli...

Participation of bacteria in weathering processes of silicates Biological processes presented by the metabolic activity of different species of bacteria adhered at the mineral surfaces are a part of the geochemical processes. These bacteria accelerate, by the production of organic acids into the minerals structural bonds, the leaching of elements and their subsequent and gradual transformation to the secondary minerals. Microbial destructions of silicates are studied in order to processing low-quality mineral raw-materials and the remediation of soils, sediments and waters contaminated by industrial pollutants. The samples of material, used in our research, were obtained at 9 deposits of non-metallic raw-materials in Slovakia. The sediment sample was taken from the area of Baikal Lake. The presence of microorganisms in the matrix most frequently was determined by a subsequent isolation of microorganisms and identification of bacterial species presented in the silicate matrix. The species of Bacillus and Pseudomonas genus were the common representative of the microorganisms.

We investigated the relationship among environmental variables, composition, and structure of bacterial communities in different habitats in a mangrove located nearby to an oil exploitation area, aiming to retrieve the natural pattern of bacterial communities in this ecosystem. The T-RFLP analysis showed a high diversity of bacterial populations and an increase in the bacterial richness from habitats closer to the sea and without vegetation (S1) to habitats covered byAvicennia schaueriana(S2) andRhizophora mangle(S3). Environmental variables in S1 and S2 were more similar than in S3; however, when comparing the bacterial compositions, S2 and S3 shared more OTUs between them, suggesting that the presence of vegetation is an important factor in shaping these bacterial communities.In silicoanalyses of the fragments revealed a high diversity of the class Gammaproteobacteria in the 3 sites, although in general they presented quite different bacterial composition, which is probably shaped...

We investigated magnetic susceptibility (MS) variations in hydrocarbon contaminated sediments. Our objective was to determine if MS can be used as an intrinsic bioremediation indicator due to the activity of ironreducing bacteria. A contaminated and an uncontaminated core were retrieved from a site contaminated with crude oil near Bemidji, Minnesota and subsampled for MS measurements. The contaminated core revealed enriched MS zones within the hydrocarbon smear zone, which is related to iron-reduction coupled to oxidation of hydrocarbon compounds and the vadose zone, which is coincident with a zone of methane depletion suggesting aerobic or anaerobic oxidation of methane is coupled to iron-reduction. The latter has significant implications for methane cycling. We conclude that MS can serve as a proxy for intrinsic bioremediation due to the activity of iron-reducing bacteria iron-reducing bacteria and for the application of geophysics to iron cycling studies.

Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. Recent evidence suggests, however, that AOM may also be coupled to the reduction of iron (Fe) oxides. In the Baltic Sea, the post-glacial transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) around 9-7 kyr BP (before present), resulted in the accumulation of organic-rich brackish/marine sediments overlying organic-poor limnic deposits rich in Fe oxides. Methane produced in the organic-rich layer diffuses into the lake sediments, thus allowing for the possible coupling between Fe oxide reduction and methane oxidation. Here, we combine detailed geochemical analyses of the sediment and pore water retrieved from three sites that were drilled during the IODP Baltic Sea Paleoenvironment Expedition 347 with multicomponent diagenetic modeling to study the possible role of Fe-mediated AOM as a mechanism for the apparent Fe oxide reduction in the methane-bearing lake deposits below the A/L transition. Our results reveal a complex interplay between production, oxidation and transport of methane showing that besides organoclastic Fe reduction, oxidation of downward migrating methane with Fe oxides may also explain the elevated concentrations of dissolved ferrous Fe in deep Baltic Sea sediments. Our findings imply that the transition of a lake toward a marine system could lead to reactivation of deeply buried, mostly crystalline Fe oxides in organic-poor lake deposits through reactions with downward diffusing methane from the overlying organic-rich marine sediments. Based on the geochemical profiles and numerical modeling, we propose that a potential coupling between Fe oxide reduction and methane oxidation likely affects deep Fe cycling and related biogeochemical processes, such as burial of phosphorus, in systems subject to changes in organic matter loading or bottom water salinity.

In this study, three biological sand filter (BSF) were contaminated with a synthetic iron-[1500 mg L-1 Fe(II), 500 mg L-1 Fe(III)] and sulphate-rich (6000 mg L-1 SO 2/4-) acid mine drainage (AMD) (pH = 2), for 24 days, to assess the remediation capacity and the evolution of autochthonous bacterial communities (monitored by T-RFLP and 16S rRNA gene clone libraries). To stimulate BSF bioremediation involving sulphate-reducing bacteria, a readily degradable carbon source (glucose, 8000 mg L-1) was incorporated into the influent AMD. Complete neutralization and average removal efficiencies of 81.5 (±5.6)%, 95.8 (±1.2)% and 32.8 (±14.0)% for Fe(II), Fe(III) and sulphate were observed, respectively. Our results suggest that microbial iron reduction and sulphate reduction associated with iron precipitation were the main processes contributing to AMD neutralization. The effect of AMD on BSF sediment bacterial communities was highly reproducible. There was a decrease in diversity, and notably a single dominant operational taxonomic unit (OTU), closely related to Clostridium beijerinckii, which represented up to 65% of the total community at the end of the study period.

The formation of environmentally toxic acidic waste from mining activities is a worldwide problem. Neutralization of this waste can be accomplished by physicochemical and/or biological means. In this short-term study, synthetic acid mine drainage was added to sandfilled mesocosms containing silica-dominated (quartz) sand. Glucose was added as a carbon source for microbial iron and/or sulphate reduction. Replicates contained two separate batches of sand obtained from the same quarry site. The investigations used to assess and compare the chemical and biological functioning of the replicates included system hydraulic conductivity measurements, sand chemistry, effluent chemistry and bacterial community fingerprinting. Minor differences in composition of the sand, including the levels of available nutrients and micronutrients, resulted in major differences in measured parameters. 2 Significant differences in effluent chemistry were found in systems containing different batches of sand. It was demonstrated that the characteristics of the sand and the presence of acid mine drainage impacted the bacterial community structure and function. The importance of the physical substrate on the selection of functional microbial communities in systems remediating AMD should not be underestimated. The physical substrate should be carefully selected and it may be prudent to include small-scale comparative studies in each particular setting prior to full-scale implementation.

We investigated the relationship among environmental variables, composition, and structure of bacterial communities in different habitats in a mangrove located nearby to an oil exploitation area, aiming to retrieve the natural pattern of bacterial communities in this ecosystem. The T-RFLP analysis showed a high diversity of bacterial populations and an increase in the bacterial richness from habitats closer to the sea and without vegetation (S1) to habitats covered byAvicennia schaueriana(S2) andRhizophora mangle(S3). Environmental variables in S1 and S2 were more similar than in S3; however, when comparing the bacterial compositions, S2 and S3 shared more OTUs between them, suggesting that the presence of vegetation is an important factor in shaping these bacterial communities.In silicoanalyses of the fragments revealed a high diversity of the class Gammaproteobacteria in the 3 sites, although in general they presented quite different bacterial composition, which is probably shaped...

The characteristics of the Fe(III)-chelate reductase activity have been investigated in mesophyll disks of Fesufficient and Fe-deficient sugar beet leaves. The Fe(III)chelate reductase activity of mesophyll disks was light dependent and increased markedly when the epidermis was removed. Iron(III)-citrate was photo-reduced directly by light in the absence of plant tissue. Total reductase activity was the sum of enzymatic mesophyll reduction, enzymatic reduction carried out by organelles exposed at the disk edge and reduction caused by the release of substances both by exposed mesophyll cells and at the disk edge. Compounds excreted were shown by HPLC to include organic anions, mainly oxalate, citrate and malate. When expressed on a leaf surface basis, Fe deficiency decreased the total mesophyll Fe(III)-chelate reductase activity. However, Fe-sufficient disks reduced less Fe than the Fe-deficient ones when expressed on a chlorophyll basis. The optimal pH values for Fe(III) reduction were always in the range 6.0-6.7. In control leaves Fe(III)-citrate and Fe(III)-malate were the substrates that led to the highest Fe reduction rates. In Fe-deficient leaves Fe(III)-malate led to the highest Fe reduction rates, followed by Fe(III)-EDTA and then Fe(III)-citrate. K m values for the total reductase activity, enzymatic mesophyll reduction and enzymatic reduction carried out by organelles at the disk edge were obtained.

In this study, three biological sand filter (BSF) were contaminated with a synthetic iron-[1500 mg L À1 Fe(II), 500 mg L À1 Fe(III)] and sulphate-rich (6000 mg L À1 SO 2À 4) acid mine drainage (AMD) (pH = 2), for 24 days, to assess the remediation capacity and the evolution of autochthonous bacterial communities (monitored by T-RFLP and 16S rRNA gene clone libraries). To stimulate BSF bioremediation involving sulphate-reducing bacteria, a readily degradable carbon source (glucose, 8000 mg L À1) was incorporated into the influent AMD. Complete neutralization and average removal efficiencies of 81.5 (AE5.6)%, 95.8 (AE1.2)% and 32.8 (AE14.0)% for Fe(II), Fe(III) and sulphate were observed, respectively. Our results suggest that microbial iron reduction and sulphate reduction associated with iron precipitation were the main processes contributing to AMD neutralization. The effect of AMD on BSF sediment bacterial communities was highly reproducible. There was a decrease in diversity, and notably a single dominant operational taxonomic unit (OTU), closely related to Clostridium beijerinckii, which represented up to 65% of the total community at the end of the study period.

There is a growing need for a better understanding of the biogeochemical dynamics involved in microbial U(VI) reduction due to an increasing interest in using biostimulation via electron donor addition as a means to remediate uranium contaminated sites. U(VI) reduction has been observed to be maximized during iron-reducing conditions and to decrease upon commencement of sulfate-reducing conditions. There are many unknowns regarding the impact of iron/sulfate biogeochemistry on U(VI) reduction. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the uranium biostimulation period even after sulfate reduction becomes dominant. Column experiments were conducted with Old Rifle site sediments containing Fe-oxides, Fe-clays, and sulfate rich groundwater. Half of the columns had sediment that was augmented with small amounts of Fe(III) in the form of 57 Fegoethite, allowing for a detailed tracking of minute changes of this added phase to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. Mö ssbauer spectroscopy showed that the added 57 Fe-goethite was bioreduced only during the first thirty days of biostimultuion, after which it remained constant. Augmentation with Fe(III) had a significant effect on the total flux of electrons towards different electron acceptors; it suppressed the degree of sulfate reduction, had no significant impact on Geobacter-type bacterial numbers but decreased the bacterial numbers of sulfate reducers and affected the overall microbial community composition. The addition of Fe(III) had no noticeable effect on the total uranium reduction.

Dehalorespiration bioremediation has been considered for chlorinated compound removal from two trichloroethene contaminated groundwater plumes in the OU 5 area of Hill Air Force Base, Utah. The distributions and population densities of the 16S rRNA genes of Bacteria, Dehalococcoides ethenogenes, Desulfuromonas michiganensis, Geobacter spp. and Rhodoferax ferrireducens-like bacteria, as well as the functional genes trichloroethene reductive dehalogenase (tceA) and vinyl chloride reductase (vcrA) were determined in contaminated aquifer material samples. The influence of aquifer physical and chemical properties, including iron availability, on these distributions was evaluated. Twenty aquifer cores were collected. DNA was extracted and analyzed using real-time quantitative polymerase chain reaction (RT-qPCR) to quantify the gene densities. Dehalococcoides population densities were low and unevenly distributed. D. michiganensis was found in 12 cores while Geobacter spp. were found in 8 cores. Rhodoferax ferrireducens-like bacteria were widely distributed. The vcrA gene distribution was relatively uniform and broad but the tceA gene was detectable in only 2 cores. Gene distribution was not related to core clusters derived from physical/chemical characteristics.

The Niger Delta is one of the most damaged ecosystems in the world, mainly due to petroleum contamination by oil exploration accidents. We investigated the natural attenuation potential of Niger Delta subsurface sediment samples for anaerobic hydrocarbon degradation using benzene as a model compound under iron-reducing, sulfate-reducing, and methanogenic conditions. Benzene was slowly mineralized under methanogenic and iron-reducing conditions using nitrilotriacetic acid (NTA)-Fe(III), or poorly crystalline Fe(III) oxyhydroxides as electron acceptors, analyzed by measurement of 13CO2 produced from added 13C-labelled benzene. Highest mineralization rates were observed in microcosms amended with Fe(III) oxyhydroxides. The microbial communities of benzene-mineralizing enrichment cultures were characterized by next-generation sequencing of the genes coding for 16S rRNA and methyl coenzyme M reductase A (mcrA). Abundant phylotypes were affiliated to Betaproteobacteriales, Ignavibacterial...

Iron (Fe) reduction and oxidation are important biogeochemical processes coupled to decomposition, nutrient cycling, and mineral weathering, but factors controlling their rates and spatial distribution with depth are poorly understood in terrestrial soils. In aquatic ecosystems, Fe reduction often occurs below a zone of oxic sediments. We tested an alternative conceptual model for Fe redox cycling in terrestrial soils using a deep humid tropical forest soil profile. We hypothesized that Fe reduction in

To evaluate the stability of biogenic nanoparticulate U(IV) in the presence of an Fe(II)-rich iron-bearing phyllosilicate, we examined the reduction of structural Fe(III) in chlorite CCa-2 and uranium(VI) by Shewanella oneidensis MR-1, and the reoxidation of these minerals (after pasteurization) via the introduction of oxygen. Bioreduction experiments were conducted with combinations of chlorite, U(VI), and anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify the reduction of U(VI) by chemically-reduced chlorite-associated Fe(II), the oxidation of nanoparticulate U(IV) by unaltered structural Fe(III) in chlorite, and the sorption of U(VI) to chlorite, to elucidate interactions between U(VI)/ U(IV) and Fe(II)/Fe(III)-chlorite. Solids were characterized by X-ray diffraction, scanning electron microscopy, and X-ray absorption spectroscopy to confirm Fe and U reduction and reoxidation. U(VI) enhanced the reduction of structural Fe(III) in chlorite and nanoparticulate U(IV) was oxidized by structural Fe(III) in chlorite, demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to chlorite-Fe(III). Abiotic reduction of U(VI) by chlorite-associated Fe(II) was very slow compared to biological U(VI) reduction. The rate of nanoparticulate U(IV) oxidation by dissolved oxygen increased in the presence of chlorite-associated Fe(II), but the extent of U(IV) oxidation decreased as compared to no-chlorite controls. In identical experiments conducted with bioreduced suspensions of nanoparticulate U(IV) and nontronite (another iron-bearing phyllosilicate), the rate of U(IV) oxidation by dissolved oxygen increased in the presence of nontronite-associated Fe(II). In summary, we found that structural Fe(III) in chlorite delayed the onset of U(VI) loss from solution, while chlorite-associated Fe(II) enhanced the oxidation rate of U(IV) by dissolved oxygen, indicating that chlorite-associated Fe(II) could not protect nanoparticulate U(IV) from oxygen intrusion but instead increased the oxidation rate of U(IV).

Dehalorespiration bioremediation has been considered for chlorinated compound removal from two trichloroethene contaminated groundwater plumes in the OU 5 area of Hill Air Force Base, Utah. The distributions and population densities of the 16S rRNA genes of Bacteria, Dehalococcoides ethenogenes, Desulfuromonas michiganensis, Geobacter spp. and Rhodoferax ferrireducens-like bacteria, as well as the functional genes trichloroethene reductive dehalogenase (tceA) and vinyl chloride reductase (vcrA) were determined in contaminated aquifer material samples. The influence of aquifer physical and chemical properties, including iron availability, on these distributions was evaluated. Twenty aquifer cores were collected. DNA was extracted and analyzed using real-time quantitative polymerase chain reaction (RT-qPCR) to quantify the gene densities. Dehalococcoides population densities were low and unevenly distributed. D. michiganensis was found in 12 cores while Geobacter spp. were found in 8 cores. Rhodoferax ferrireducens-like bacteria were widely distributed. The vcrA gene distribution was relatively uniform and broad but the tceA gene was detectable in only 2 cores. Gene distribution was not related to core clusters derived from physical/chemical characteristics.

Oxygen (O2) limitation is generally understood to suppress soil carbon (C) decomposition and is a key mechanism impacting terrestrial C stocks under global change. Yet, O2 limitation may differentially impact kinetic or thermodynamic vs. physico-chemical C protection mechanisms, challenging our understanding of how soil C may respond to climate-mediated changes in O2 dynamics. Although O2 limitation may suppress decomposition of new litter C inputs, release of physico-chemically protected C due to iron (Fe) reduction could potentially sustain soil C losses. To test this tradeoff, we incubated two disparate upland soils that experience periodic O2 limitation-a tropical rainforest Oxisol and a temperate cropland Mollisol-with added litter under either aerobic (control) or anaerobic conditions for one year. Anoxia suppressed total C loss by 27% in the Oxisol and by 41% in the Mollisol relative to the control, mainly due to the decrease in litter-C decomposition. However, anoxia sustained or even increased decomposition of native soil-C (11.0% vs. 12.4% in the control for the Oxisol and 12.5% vs. 5.3% in the control for the Mollisol, in terms of initial soil C mass), and it stimulated losses of metal-or mineralassociated C. Solid-state 13C nuclear magnetic resonance spectroscopy demonstrated that anaerobic conditions decreased protein-derived C but increased lignin-and carbohydrate-C relative to the control. Our results indicate a tradeoff between physico-chemical and kinetic/thermodynamic C protection mechanisms under anaerobic conditions, whereby decreased decomposition of litter C was compensated by more extensive loss of mineral-associated soil C in both soils. This challenges the common assumption that anoxia inherently protects soil C and illustrates the vulnerability of mineral-associated C under anaerobic events characteristic of a warmer and wetter future climate.

To evaluate the stability of biogenic nanoparticulate U(IV) in the presence of an Fe(II)-rich iron-bearing phyllosilicate, we examined the reduction of structural Fe(III) in chlorite CCa-2 and uranium(VI) by Shewanella oneidensis MR-1, and the reoxidation of these minerals (after pasteurization) via the introduction of oxygen. Bioreduction experiments were conducted with combinations of chlorite, U(VI), and anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify the reduction of U(VI) by chemically-reduced chlorite-associated Fe(II), the oxidation of nanoparticulate U(IV) by unaltered structural Fe(III) in chlorite, and the sorption of U(VI) to chlorite, to elucidate interactions between U(VI)/ U(IV) and Fe(II)/Fe(III)-chlorite. Solids were characterized by X-ray diffraction, scanning electron microscopy, and X-ray absorption spectroscopy to confirm Fe and U reduction and reoxidation. U(VI) enhanced the reduction of structural Fe(III) in chlorite and nanoparticulate U(IV) was oxidized by structural Fe(III) in chlorite, demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to chlorite-Fe(III). Abiotic reduction of U(VI) by chlorite-associated Fe(II) was very slow compared to biological U(VI) reduction. The rate of nanoparticulate U(IV) oxidation by dissolved oxygen increased in the presence of chlorite-associated Fe(II), but the extent of U(IV) oxidation decreased as compared to no-chlorite controls. In identical experiments conducted with bioreduced suspensions of nanoparticulate U(IV) and nontronite (another iron-bearing phyllosilicate), the rate of U(IV) oxidation by dissolved oxygen increased in the presence of nontronite-associated Fe(II). In summary, we found that structural Fe(III) in chlorite delayed the onset of U(VI) loss from solution, while chlorite-associated Fe(II) enhanced the oxidation rate of U(IV) by dissolved oxygen, indicating that chlorite-associated Fe(II) could not protect nanoparticulate U(IV) from oxygen intrusion but instead increased the oxidation rate of U(IV).

Subsurface-flow constructed wetlands (CW) with charcoal-or slag-based bed matrices were investigated for their potential use in remediating acid mine drainage (AMD). A CW is effectively a reactor in which some components of the wastewater are broken down by the organisms occurring within the CW, whilst others may be degraded by physico-chemical processes or a combination thereof. Two 200 ℓ small-scale CWs were built at the University. Commercially available charcoal and <19 mm basic oxygen furnace (BOF) slag were used as the bed matrices and the units were planted with a variety of plants. The units were exposed to an artificial AMD. The results showed that the systems removed almost all soluble iron and more than 75% of the sulphate. Both CWs were able to increase the pH of the AMD.

Charge and softness of the outer part of the cell wall of Thiobacillus ferrooxidans in the low ionic strength medium The surface charge and surface potential are parameters influencing the microbial adhesion phenomenon through the electrostatic interaction between bacteria and substrates. The Smoluchowski equation, originally developed for estimating the above parameters from the experimentally accessible electrophoretic mobility of rigid colloid particles, is however inapplicable to the elastic bacterial cells. The problem is that the outer cell wall of bacteria is a layer with a complex polyelectrolyte structure. In this article, the Ohshima´s model of the "soft" particle is applied to describe the surface electrostatics of Thiobacillus ferrooxidans cells by measuring their electrophoretic mobility in distilled water as a function of a (low) ionic strength and pH. In this model, the rigid core is considered to be covered with a charged ionpenetrable layer of polyelectrolytes. Two model parameters have been determined by the curve fitting at pH from 3.2 to 5.8, namely the number density of the dissociated groups N and the softness parameter 1/λ of the polyelectrolyte layer of the bacterium. A disagreement of the best fit parameters (evaluated by the correlation coefficient) with the analogous parameters determined for other colloids (including bacterial cells) in aqueous solutions of a high ionic strength is discussed.

Influence of Mechanical Activation on the selectivity of Bornite Leaching Sulfidic mineral bornit Cu 5 FeS 4 was exposed to the selective leaching of copper in H 2 SO 4 solution. Surface changes of the mechanically activated sulphide were investigated before and after leaching using the infrared spectroscopy and the scanning electron microscopy. The mechanical activation of the mineral resulted in the mechanochemical surface oxidation and in the formation of the carbonates and sulphates. Furthermore, the specific area and the disordering of the mineral crystal structure increased. These aspects influence the kinetic and selectivity of acid leaching of bornite. Acid leaching of mechanically activated bornite follows through the two stages. In the first, rapid stage of leaching, the simple dissolution of products occurs (iron carbonate, copper and iron sulphate), which are situated in the surface layer of mechanically activated bornite. A relatively high iron recovery is due to the dissolution of hematite which is a minor component of bornite. The second, slow stage of leaching represents leaching of minerals. Iron do not practically underlies to the leaching and the recovery of copper increases gradually. The leaching selectivity of bornite is defined by the ratio Cu/Fe and increases with the growing time of mechanical activation, but only to 10 minutes. Subsequently, an additional increase of the time of mechanical activation tends to decrease the selectivity what is probably caused by the effect of the reduction of reaction surface processes due to agglomeration effects pending the milling and the formation of sulphur on the surfaces of particles which restricted the access of reagents to the remaining mineral. Moreover, this fact was observed by the SEM analysis of bornite. The interdependence between the leaching selectivity of bornite and specific surface area indicates a direct effect of the surface deformation of mechanically activated bornite on the selectivity of leaching.

NAD(P)H quinone oxidoreductase 1 is involved in antioxidant defence and protection from cancer, stabilizing the apoptosis regulator p53 towards degradation. Here, we studied the enzymological, biochemical and biophysical properties of two cancer-associated variants (p.R139W and p.P187S). Both variants (especially p.187S) have lower thermal stability and greater susceptibility to proteolysis compared to the wild-type. p.P187S also has reduced activity due to a lower binding affinity for the FAD cofactor as assessed by activity measurements and direct titrations. Native gel electrophoresis and dynamic light scattering also suggest that p.P187S has a higher tendency to populate unfolded states under native conditions. Detailed thermal stability studies showed that all variants irreversibly denature causing dimer dissociation, while addition of FAD restores the stability of the polymorphic forms to wild-type levels. The kinetic destabilization induced by polymorphisms as well as the kin...

In the course of an investigation of alkaliphilic iron reduction, metabiotic interactions in a binary culture reducing synthetic ferrihydrite (SF) have been studied. The binary culture contained two anaerobic bacteria: the alkaliphilic organotrophic bacillus Anaerobacillus alkalilacustris, which ferments sugars and sugar alcohols and is incapable of iron reduction, and the dissimilatory iron reducing bacterium Geoalkali bacter ferrihydriticus, which is able to grow on acetate at the expense of anaerobic respiration. The experi ments were performed under conditions of SF excess and deficiency. It was expected that G. ferrihydriticus would oxidize the acetate formed in the course of mannitol fermentation by A. alkalilacustris. The results were different from the expected ones: in the binary culture, fermentation products other than acetate were used for iron reduction; these were primarily formate and ethanol, which led to acetate accumulation rather than consumption. The reduction of SF to magnetite and/or siderite followed the earlier established regularities. The preferential order of donor utilization by G. ferrihydriticus did not conform to the energy yields of the cor responding reactions. Thus, it has been shown that there may be interactions in microbial communities that cannot be predicted from the characteristics of pure cultures. The degradation pathways of organic matter in communities may differ considerably from those observed in pure cultures, even in pure cultures of highly specialized organisms.

Type II NADH:quinone oxidoreductase (NDH-2) is central to the respiratory chains of many organisms. It is not present in mammals so may be exploited as an antimicrobial drug target or used as a substitute for dysfunctional respiratory complex I in neuromuscular disorders. NDH-2 is a single-subunit monotopic membrane protein with just a flavin cofactor, yet no consensus exists on its mechanism. Here, we use steady-state and pre-steady-state kinetics combined with mutagenesis and structural studies to determine the mechanism of NDH-2 from Caldalkalibacillus thermarum. We show that the two substrate reactions occur independently, at different sites, and regardless of the occupancy of the partner site. We conclude that the reaction pathway is determined stochastically, by the substrate/product concentrations and dissociation constants, and can follow either a ping-pong or ternary mechanism. This mechanistic versatility provides a unified explanation for all extant data and a new foundat...

Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. Recent evidence suggests, however, that AOM may also be coupled to the reduction of iron (Fe) oxides. In the Baltic Sea, the post-glacial transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) around 9-7 kyr BP (before present), resulted in the accumulation of organic-rich brackish/marine sediments overlying organic-poor limnic deposits rich in Fe oxides. Methane produced in the organic-rich layer diffuses into the lake sediments, thus allowing for the possible coupling between Fe oxide reduction and methane oxidation. Here, we combine detailed geochemical analyses of the sediment and pore water retrieved from three sites that were drilled during the IODP Baltic Sea Paleoenvironment Expedition 347 with multicomponent diagenetic modeling to study the possible role of Fe-mediated AOM as a mechanism for the apparent Fe oxide reduction in the methane-bearing lake deposits below the A/L transition. Our results reveal a complex interplay between production, oxidation and transport of methane showing that besides organoclastic Fe reduction, oxidation of downward migrating methane with Fe oxides may also explain the elevated concentrations of dissolved ferrous Fe in deep Baltic Sea sediments. Our findings imply that the transition of a lake toward a marine system could lead to reactivation of deeply buried, mostly crystalline Fe oxides in organic-poor lake deposits through reactions with downward diffusing methane from the overlying organic-rich marine sediments. Based on the geochemical profiles and numerical modeling, we propose that a potential coupling between Fe oxide reduction and methane oxidation likely affects deep Fe cycling and related biogeochemical processes, such as burial of phosphorus, in systems subject to changes in organic matter loading or bottom water salinity.

Additional file 4: Table S4. Summary of microbial community composition detected in Probe Lake (PL-M) bioreactors on day 58, 85, 98 and 128 using 16S rRNA gene sequencing. Day 0 microbial mat sample is taken from the initial inoculation. Numbers indicate proportion of reads with a &gt;1% average relative abundance in an OTU compared to all OTUs listed on a per sample basis. Closest cultured relative as determined by BLAST search is shown.

We investigated magnetic susceptibility (MS) variations in hydrocarbon contaminated sediments. Our objective was to determine if MS can be used as an intrinsic bioremediation indicator due to the activity of ironreducing bacteria. A contaminated and an uncontaminated core were retrieved from a site contaminated with crude oil near Bemidji, Minnesota and subsampled for MS measurements. The contaminated core revealed enriched MS zones within the hydrocarbon smear zone, which is related to iron-reduction coupled to oxidation of hydrocarbon compounds and the vadose zone, which is coincident with a zone of methane depletion suggesting aerobic or anaerobic oxidation of methane is coupled to iron-reduction. The latter has significant implications for methane cycling. We conclude that MS can serve as a proxy for intrinsic bioremediation due to the activity of iron-reducing bacteria iron-reducing bacteria and for the application of geophysics to iron cycling studies.

In this study, three biological sand filter (BSF) were contaminated with a synthetic iron-[1500 mg L À1 Fe(II), 500 mg L À1 Fe(III)] and sulphate-rich (6000 mg L À1 SO 2À 4) acid mine drainage (AMD) (pH = 2), for 24 days, to assess the remediation capacity and the evolution of autochthonous bacterial communities (monitored by T-RFLP and 16S rRNA gene clone libraries). To stimulate BSF bioremediation involving sulphate-reducing bacteria, a readily degradable carbon source (glucose, 8000 mg L À1) was incorporated into the influent AMD. Complete neutralization and average removal efficiencies of 81.5 (AE5.6)%, 95.8 (AE1.2)% and 32.8 (AE14.0)% for Fe(II), Fe(III) and sulphate were observed, respectively. Our results suggest that microbial iron reduction and sulphate reduction associated with iron precipitation were the main processes contributing to AMD neutralization. The effect of AMD on BSF sediment bacterial communities was highly reproducible. There was a decrease in diversity, and notably a single dominant operational taxonomic unit (OTU), closely related to Clostridium beijerinckii, which represented up to 65% of the total community at the end of the study period.

Quinone oxidoreductase activities dependent on pyridine nucleotides are associated with the plasma membrane (PM) in zucchini (Cucurbita pepo L.) hypocotyls. In the presence of NADPH, lipophilic ubiquinone homologs with up to three isoprenoid units were reduced by intact PM vesicles with a Km of 2 to 7 [mu]M. Affinities for both NADPH and NADH were similar (Km of 62 and 51 [mu]M, respectively). Two NAD(P)H:quinone oxidoreductase forms were identified. The first, labeled as peak I in gel-filtration experiments, behaves as an intrinsic membrane complex of about 300 kD, it slightly prefers NADH over NADPH, it is markedly sensitive to the inhibitor diphenylene iodonium, and it is active with lipophilic quinones. The second form (peak II) is an NADPH-preferring oxidoreductase of about 90 kD, weakly bound to the PM. Peak II is diphenylene iodonium-insensitive and resembles, in many properties, the soluble NAD(P)H:quinone oxidoreductase that is also present in the same tissue. Following pur...

Bacterial remediation of heavy metal polluted soil and effluent from paper mill was investigated using standard analytical methods. The paper mill was visited for 6 months at interval of 30 days to collect soil and effluent samples for the analysis. The pH of soil was slightly alkaline while effluent was acidic. There was a significant increase (P &lt; 0.05) in total organic carbon (TOC) of soil; and turbidity, biochemical oxygen demand (BOD), chemical oxygen demand (COD) and TOC of effluent when compared to control. Bacteria isolated from the samples were grouped into two and used to remediate eight heavy metals. The remediation experiment consists of three treatments; Treatment 1 (treated with proteobacteria), Treatment 2 (treated with non-proteobacteria) and Treatment 3 (without bacteria) (control experiment). Result of the remediation study showed that there was a significant decrease (P &lt; 0.05) in Treatment 1 and Treatment 2 of all the heavy metals in soil and effluent sampl...

We investigated magnetic susceptibility (MS) variations in hydrocarbon contaminated sediments. Our objective was to determine if MS can be used as an intrinsic bioremediation indicator due to the activity of ironreducing bacteria. A contaminated and an uncontaminated core were retrieved from a site contaminated with crude oil near Bemidji, Minnesota and subsampled for MS measurements. The contaminated core revealed enriched MS zones within the hydrocarbon smear zone, which is related to iron-reduction coupled to oxidation of hydrocarbon compounds and the vadose zone, which is coincident with a zone of methane depletion suggesting aerobic or anaerobic oxidation of methane is coupled to iron-reduction. The latter has significant implications for methane cycling. We conclude that MS can serve as a proxy for intrinsic bioremediation due to the activity of iron-reducing bacteria iron-reducing bacteria and for the application of geophysics to iron cycling studies.

Both industrial effluent discharge and the resuspension of contaminated marine sediments are important sources of trace metals in seawater which potentially affect marine ecosystems. The aim of this study was to evaluate the impact of the industrial wastewaters having acidic pH (2-3) and containing trace metals on microbial diversity in the coastal ecosystem of the Gulf of Gabès (Tunisia, southern Mediterranean Sea) subjected to resuspension events of marine sediments. Four trace elements (As, Cd, U, and V) were monitored during 10-day sediment resuspension experiments. The highest enrichment in the seawater dissolved phase was observed for Cd followed by U, V, and As. Cd remobilization was improved by indigenous microbial community, while U release was mainly abiotic. Acidic effluent addition impacted both trace metal distribution and microbial diversity, particularly that of the abundant phylum Bacteroidetes. Members of the order Saprospirales were enriched from sediment in natural seawater (initial pH > 8), while the family Flavobacteriaceae was favored by acidified seawater (initial pH < 8). Some Flavobacteriaceae members were identified as dominant species in both initial sediment and experiments with acidic wastewater, in which their relative abundance increased with increasing dissolved Cd levels. It could be therefore possible to consider them as bioindicators of metal pollution and/or acidification in marine ecosystems.

The amino acid sequence of mouse liver NAD(P)H:quinone acceptor oxidoreductase (EC 1.6.99.2) has been determined by tandem mass spectrometry and deduced from the nucleotide sequence of the cDNA encoding for the enzyme. The electrospray mass spectral analyses revealed, as previously reported (Prochaska HJ, Talalay P, 1986, J Biol Chem 261: 1372-1378), that the 2 forms-the hydrophilic and hydrophobic forms-of the mouse liver quinone reductase have the same molecular weight. No amino acid sequence differences were found by tandem mass spectral analyses of tryptic peptides of the 2 forms. Moreover, the amino-termini of the mouse enzymes are acetylated as determined by tandem mass spectrometry. Further, only 1 cDNA species encoding for the quinone reductase was found. These results suggest that the 2 forms of the mouse quinone reductase have the same primary sequences, and that any difference between the 2 forms may be attributed to a labile posttranslational modification. Analysis of the mouse quinone reductase cDNA revealed that the enzyme is 273 amino acids long and has a sequence homologous to those of rat and human quinone reductases. In this study, the mouse quinone reductase cDNA was also ligated into a prokaryotic expression plasmid pKK233.2, and the constructed plasmid was used to transform Escherichia coli strain JM109. The E. coli-expressed mouse quinone reductase was purified and characterized. Although mouse quinone reductase has an amino acid sequence similar to those of the rat and human enzymes, the mouse enzyme has a higher NAD(P)H-menadione reductase activity and is less sensitive to flavones and dicoumarol, 2 known inhibitors of the enzyme. The results would indicate that the regions in mouse quinone reductase that contain amino acids different from the rat and human enzymes are critical for the binding of menadione, flavones, and dicoumarol.

We investigated the relationship among environmental variables, composition, and structure of bacterial communities in different habitats in a mangrove located nearby to an oil exploitation area, aiming to retrieve the natural pattern of bacterial communities in this ecosystem. The T-RFLP analysis showed a high diversity of bacterial populations and an increase in the bacterial richness from habitats closer to the sea and without vegetation (S1) to habitats covered byAvicennia schaueriana(S2) andRhizophora mangle(S3). Environmental variables in S1 and S2 were more similar than in S3; however, when comparing the bacterial compositions, S2 and S3 shared more OTUs between them, suggesting that the presence of vegetation is an important factor in shaping these bacterial communities.In silicoanalyses of the fragments revealed a high diversity of the class Gammaproteobacteria in the 3 sites, although in general they presented quite different bacterial composition, which is probably shaped...

Acid mine drainages (AMDs) arise at the weathering of sulphidic minerals. The occurrence of acidic streams is commonly associated with the human mining activities. Due to the disruption and excavation of sulphide deposits, the oxidation processes have initiated. Acidic products of sulphide oxidation accelerate the degradation of accompanying minerals. AMDs typically contain high concentrations of sulfuric acid and soluble metals and cause serious ecological problems due to the water pollution and the devastation of adjacent country. Microbial life in these extremely acidic environments may be considerably diverse. AMDs are abundant in bacteria capable to oxidize and/or to reduce iron. The rate of bacterial oxidation of ferrous iron released from pyrite surfaces is up to one million times faster than the chemical oxidation rate at low pH. Bacterial regeneration of ferric iron maintains the continuity of pyrite oxidation and the production of AMDs. Another group of microorganisms livi...

Heterotrophic bacteria proliferate in organic-rich environments and systems containing sufficient essential nutrients. Nitrogen, phosphorus and potassium are the nutrients required in the highest concentrations. The ratio of carbon to nitrogen is an important consideration for wastewater bioremediation because insufficient nitrogen may result in decreased treatment efficiency. It has been shown that during the treatment of effluent from the pulp and paper industry, bacterial nitrogen fixation can supplement the nitrogen requirements of suspended growth systems. This study was conducted using physicochemical analyses and culture-dependent and -independent techniques to ascertain whether nitrogen-fixing bacteria were selected in biological sand filters used to treat synthetic winery wastewater with a high carbon to nitrogen ratio (193:1). The systems performed well, with the influent COD of 1351 mg/L being reduced by 84-89%. It was shown that the nitrogen fixing bacterial population w...

NAD(P)H:quinone oxidoreductase 1 (NQO1) is a flavoenzyme upregulated in response to oxidative stress and in some cancers. Its upregulation by compounds has been used as an indicator of their potential anti-cancer properties. In this study we have designed, produced and tested a fluorogenic coumarin conjugate which selectively releases highly fluorescent 4-methylumbelliferone (4-MU) in the presence of NQO1. It was found that measuring 4-MU release rapidly and specifically quantitated NQO1 levels in vitro and in live cells. Both the substrate and its products freely perfused through cell membranes and were non-toxic. The substrate was very specific with low background, and the assay itself could be done in less than 10 minutes. This is the first assay to allow the quantitation of NQO1 in live cells which can then be retained for further experiments.

show differential enzyme activities towards hydrophilic or hydrophobic ubiquinone homologs. By chromatography on phenyl Sepharose, we purified the two isoforms from pig liver cytosol and measured their reduction of several ubiquinone homologs of different side chain length. We also studied by electron paramagnetic resonance the effect of NAD(P)H:(quinone acceptor) oxidoreductase 1 on steadystate levels of chromanoxyl radicals generated by linoleic acid and lipooxygenase and confirmed the enzyme's ability to protect alphatocopherol against oxidation induced with H 2 O 2-Fe 2+. Our results demonstrated that the different hydrophobicities of the isoforms do not reflect different reactivities towards ubiquinones of different side chain length. In addition, electron paramagnetic resonance studies showed that in systems containing the reductase plus NADH, levels of chromanoxyl radicals were dramatically reduced. Morever, in the presence of oxidants, alpha-tocopherol was preserved by NAD(P)H:(quinone acceptor) oxidoreductase 1, supporting our hypothesis that regeneration of alpha-tocopherol may be one of the physiologic functions of this enzyme.

The transition metal iron is an important element for the sustenance of life-it can function either as an electron acceptor or as a donor and serves as a cofactor in many enzymes activities. The cytoplasmic NAD(P)H-dependent ferric reductase in Thermus scotoductus SA-01 shares high sequence and structural similarity to prokaryotic thioredoxin reductases. Here we report the sequence of the ferric reductase (which is typically annotated as a thioredoxin reductase-like protein) and a comparative kinetic study with the thioredoxin reductase from SA-01. Structurally, the most noteworthy difference, immediately apparent from the protein sequence, is the absence of the disulphide redox centre in the ferric reductase. This is the first report relating the attributes of such a redox protein to its ability to reduce a ferric substrate.

Both industrial effluent discharge and the resuspension of contaminated marine sediments are important sources of trace metals in seawater which potentially affect marine ecosystems. The aim of this study was to evaluate the impact of the industrial wastewaters having acidic pH (2-3) and containing trace metals on microbial diversity in the coastal ecosystem of the Gulf of Gabès (Tunisia, southern Mediterranean Sea) subjected to resuspension events of marine sediments. Four trace elements (As, Cd, U, and V) were monitored during 10-day sediment resuspension experiments. The highest enrichment in the seawater dissolved phase was observed for Cd followed by U, V, and As. Cd remobilization was improved by indigenous microbial community, while U release was mainly abiotic. Acidic effluent addition impacted both trace metal distribution and microbial diversity, particularly that of the abundant phylum Bacteroidetes. Members of the order Saprospirales were enriched from sediment in natural seawater (initial pH > 8), while the family Flavobacteriaceae was favored by acidified seawater (initial pH < 8). Some Flavobacteriaceae members were identified as dominant species in both initial sediment and experiments with acidic wastewater, in which their relative abundance increased with increasing dissolved Cd levels. It could be therefore possible to consider them as bioindicators of metal pollution and/or acidification in marine ecosystems.