text:
Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.
Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M
A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.
Volatile fatty acids as substrates for iron and sulfate reduction in Arctic marine sediments, Svalbard
Finke, N.; Vandieken, V.; Jorgensen, B. B.
Anaerobic degradation of complex organic material in aquatic systems is a multi-step process. The metabolic products of fermentative bacteria serve as electron donors for the terminal oxidizing bacteria. In marine sediments, iron reduction and sulfate reduction are generally the most important terminal oxidation processes in the upper anoxic zone [1]. Microorganisms that reduce iron and sulfate may use a broad range of electron donors, yet the list of potential substrates provides little information about the substrates used in situ by these organisms. Investigations on the electron donors for sulfate reducers in marine sediments have shown that volatile fatty acids (VFA), and in particular acetate, together with hydrogen are the major substrates (e.g. [2-4]). Similar investigations for iron reduction or simultaneous iron and sulfate reduction are lacking for marine sediments. Furthermore, most of these studies were made in temperate sediments and little is known about the substrates for sulfate reducers in permanently cold sediments, which account for >90% of the ocean floor [5]. We investigated the relative contributions of iron reduction and sulfate reduction to the terminal oxidation of organic carbon and the importance of acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in permanently cold, Arctic sediments from Svalbard. In the surface layer (0-2 cm) sulfate reduction accounted for 2/3 of the organic carbon oxidation (determined as DIC production), the remaining 1/3 were attributed to iron reduction. In the 5-9 cm layer sulfate reduction was the sole important terminal oxidation step. The contribution of acetate to terminal oxidation was determined by radiotracer incubation as well as from the accumulation after the inhibition of sulfate reduction by selenate. The rates determined with the two methods varied by less than 20%. Acetate turnover, determined with the tracer incubations, accounted for 10 and 40% of
Acetate, lactate, propionate, and isobutyrate as electron donors for iron and sulfate reduction in Arctic marine sediments, Svalbard
DEFF Research Database (Denmark)
Finke, Niko; Vandieken, Verona; Jørgensen, Bo Barker
The contribution of volatile fatty acids (VFA) as e--donors for anaerobic terminal oxidation of organic carbon through iron and sulfate reduction was studied in Arctic fjord sediment. Dissolved inorganic carbon, Fe2+, VFA concentrations, and sulfate reduction were monitored in slurries from...... by alternative e--donors. The accumulation of VFA in the selenate-inhibited 0-2 cm slurry did not enhance iron reduction, indicating that iron reducers were not limited by VFA availability....
The anaerobic degradation of organic matter in Danish coastal sediments: iron reduction, manganese reduction, and sulfate reduction
DEFF Research Database (Denmark)
Canfield, Donald Eugene; Thamdrup, B; Hansen, Jens Würgler
). In the deep portion of the basin, surface Mn enrichments reached 3.5 wt%, and Mn reduction was the only important anaerobic carbon oxidation process in the upper 10 cm of the sediment. In the less Mn-rich sediments from intermediate depths in the basin, Fe reduction ranged from somewhat less, to far more...... speculate that in shallow sediments of the Skagerrak, surface Mn oxides are present in a somewhat reduced oxidation level (deep basin....
In situ redox manipulation of subsurface sediments from Fort Lewis, Washington: Iron reduction and TCE dechlorination mechanisms
Energy Technology Data Exchange (ETDEWEB)
JE Szecsody; JS Fruchter; DS Sklarew; JC Evans
Pacific Northwest National Laboratory (PNNL) conducted a bench-scale study to determine how effective chemically treated Ft. Lewis sediments can degrade trichloroethylene (TCE). The objectives of this experimental study were to quantify: (1) sediment reduction and oxidation reactions, (2) TCE degradation reactions, and (3) other significant geochemical changes that occurred. Sediment reduction and oxidation were investigated to determine the mass of reducible iron in the Ft. Lewis sediments and the rate of this reduction and subsequent oxidation at different temperatures. The temperature dependence was needed to be able to predict field-scale reduction in the relatively cold ({approximately}11 C) Ft. Lewis aquifer. Results of these experiments were used in conjunction with other geochemical and hydraulic characterization to design the field-scale injection experiment and predict barrier longevity. For example, the sediment reduction rate controls the amount of time required for the dithionite solution to fully react with sediments. Sediment oxidation experiments were additionally conducted to determine the oxidation rate and provide a separate measure of the mass of reduced iron. Laboratory experiments that were used to meet these objectives included: (1) sediment reduction in batch (static) systems, (2) sediment reduction in 1-D columns, and (3) sediment oxidation in 1-D columns. Multiple reaction modeling was conducted to quantify the reactant masses and reaction rates.
Evidence for the Occurrence of Microbial Iron Reduction in Bulk Aerobic Unsaturated Sediments
Cooper, D. C.; Kukkadapu, R. K.; Smith, W. A.; Fox, D. T.; Plummer, M. A.; Hull, L. C.
Radionuclide transport experiments conducted in a large, meso-scale column reactor (MSCR, 10 ft high x 3 ft dia) operated under unsaturated flow conditions with simulated rainwater influent provide evidence that microbial iron reduction can occur in bulk-aerobic vadose zone systems with a low organic carbon content (~0.5 wt%). Soil gas analyses indicate that CO2 varied between ~0.1% of soil gas (top) and 12% to 18% of soil gas (bottom). O2 varied inversely with CO2, and the ratio of (CO2 produced) / (O2 consumed) was 0.8 +/- 0.1. NO3- was present at high concentrations, and originated from soluble NO3- salts present in the packing material. Ammonia was present at low levels, and limited NO2- production was observed. There was no increase in aqueous iron, and methane and sulfide were not produced. M\\H{o}ssbauer analyses of sediment iron mineralogy indicate that the sedimentary iron in the packing material is 63% illite Fe(III), 16% illite Fe(II), 13% hematite, and 8% poorly-crystalline/small-particulate (pc/sp) iron oxide. Sediments collected from the lower portion of the column (5.5 fbs, feet below surface) still contain illite and hematite, but have lost the pc/sp iron oxide component. The Fe(III)/Fe(II) ratio of the illite appears to be unchanged at this depth. Analyses of sediment extractable DNA and cell number indicate that bacterial abundances increase from the surface to 0.5 fbs, and then remain constant with depth. Initial results from DGGE and 16s rDNA clone libraries indicate that microbial community structure alters with increasing depth, decreasing O2 content, and loss of pc/sp iron oxides. These data indicate a predominance of Clostridium at the column top, with Bacillus, Desulfobacterium, and Pseudomonas also providing a significant contribution. At 0.5 fbs, Clostridium represents a larger fraction of the total community with Desulfobacterium present as the second most abundant component. By 5.5 fbs, Clostridium is a minor component and the community
The incorporation of reductive transformations into environmental fate models requires the characterization of natural reductants in well-characterized sediments and aquifer materials. For this purpose, reactivity patterns (i.e., the range and relative order of reactivity) for a...
Iron oxide reduction in methane-rich deep Baltic Sea sediments
DEFF Research Database (Denmark)
Egger, Matthias; Hagens, Mathilde; Sapart, Celia J.
/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...... 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....
Microbial iron reduction and methane oxidation in subsurface sediments of the Arabian Sea
Digital Repository Service at National Institute of Oceanography (India)
Fernandes, C.E.G.; Judith, M.; Gonsalves, M.J.B.D.; Nazareth, D.R.; Nagarchi, L.; Kamaleson, A.S.
as it has productivity driven seasonal pattern of dioxygen-deficient waters. It is one of the most biologically productive regions of the world's ocean having a characteristic seasonal upwelling followed by the production of an oxygen minimum zone... in the water body (Wyrtki, 1971; Madhupratap et al., 1996; Naidu, 1998). The seasonal upwelling in return has been reported to have prolonged and distinct effect on biological production and sedimentation (Madhupratap et al., 1996). Another important feature...
Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.
Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li
Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.
Microbial reduction of iron ore
Hoffmann, M.R.; Arnold, R.G.; Stephanopoulos, G.
A process is provided for reducing iron ore by treatment with microorganisms which comprises forming an aqueous mixture of iron ore, microorganisms operable for reducing the ferric iron of the iron ore to ferrous iron, and a substrate operable as an energy source for the microbial reduction; and maintaining the aqueous mixture for a period of time and under conditions operable to effect the reduction of the ore. Preferably the microorganism is Pseudomonas sp. 200 and the reduction conducted anaerobically with a domestic wastewater as the substrate. An aqueous solution containing soluble ferrous iron can be separated from the reacted mixture, treated with a base to precipitate ferrous hydroxide which can then be recovered as a concentrated slurry. 11 figs.
Influence of iron redox transformations on plutonium sorption to sediments
Energy Technology Data Exchange (ETDEWEB)
Hixon, A.E.; Powell, B.A. [Environmental Engineering and Earth Sciences, Clemson Univ., Clemson, SC (United States); Hu, Y.J.; Nitsche, H. [Dept. of Chemistry, Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States); Kaplan, D.I. [Savannah River National Lab., Aiken, SC (United States); Kukkadapu, R.K.; Qafoku, O. [Pacific Northwest National Lab., Richland, WA (United States)
Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and reduction. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (hydroxylamine hydrochloride and dithionite-citrate-bicarbonate (DCB)) to selectively leach and/or reduce iron oxide and phyllosilicate/clay Fe(III). {sup 57}Fe-Moessbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides and reduction of phyllosilicate Fe(III). {sup 57}Fe-Moessbauer spectroscopy showed that the Fe-mineral composition of the untreated sediment is: 25-30% hematite, 60-65% small-particle/Al-goethite, and < 10% Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate-bicarbonate buffer), much of the hematite and goethite was removed. Partial reduction of phyllosilicate Fe(III) was evident in the sediments subjected to DCB treatment. Sorption of Pu(V) was monitored over one week for the untreated and each of five treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. The rate of sorption appears to correlate with the fraction of Fe(II) in the sediment (untreated or treated). Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu
Rock magnetic and geochemical evidence for authigenic magnetite formation via iron reduction in coal-bearing sediments offshore Shimokita Peninsula, Japan (IODP Site C0020)
Phillips, Stephen C.; Johnson, Joel E.; Clyde, William C.; Setera, Jacob B.; Maxbauer, Daniel P.; Severmann, Silke; Riedinger, Natascha
Sediments recovered at Integrated Ocean Drilling Program (IODP) Site C0020, in a fore-arc basin offshore Shimokita Peninsula, Japan, include numerous coal beds (0.3-7 m thick) that are associated with a transition from a terrestrial to marine depositional environment. Within the primary coal-bearing unit (˜2 km depth below seafloor) there are sharp increases in magnetic susceptibility in close proximity to the coal beds, superimposed on a background of consistently low magnetic susceptibility throughout the remainder of the recovered stratigraphic sequence. We investigate the source of the magnetic susceptibility variability and characterize the dominant magnetic assemblage throughout the entire cored record, using isothermal remanent magnetization (IRM), thermal demagnetization, anhysteretic remanent magnetization (ARM), iron speciation, and iron isotopes. Magnetic mineral assemblages in all samples are dominated by very low-coercivity minerals with unblocking temperatures between 350 and 580°C that are interpreted to be magnetite. Samples with lower unblocking temperatures (300-400°C), higher ARM, higher-frequency dependence, and isotopically heavy δ56Fe across a range of lithologies in the coal-bearing unit (between 1925 and 1995 mbsf) indicate the presence of fine-grained authigenic magnetite. We suggest that iron-reducing bacteria facilitated the production of fine-grained magnetite within the coal-bearing unit during burial and interaction with pore waters. The coal/peat acted as a source of electron donors during burial, mediated by humic acids, to supply iron-reducing bacteria in the surrounding siliciclastic sediments. These results indicate that coal-bearing sediments may play an important role in iron cycling in subsiding peat environments and if buried deeply through time, within the subsequent deep biosphere.
Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.
Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P
Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.
Arsenic(V) reduction in relation to Iron(III) transformation and molecular characterization of the structural and functional microbial community in sediments of a basin-fill aquifer in Northern Utah.
Mirza, Babur S; Muruganandam, Subathra; Meng, Xianyu; Sorensen, Darwin L; Dupont, R Ryan; McLean, Joan E
Basin-fill aquifers of the Southwestern United States are associated with elevated concentrations of arsenic (As) in groundwater. Many private domestic wells in the Cache Valley Basin, UT, have As concentrations in excess of the U.S. EPA drinking water limit. Thirteen sediment cores were collected from the center of the valley at the depth of the shallow groundwater and were sectioned into layers based on redoxmorphic features. Three of the layers, two from redox transition zones and one from a depletion zone, were used to establish microcosms. Microcosms were treated with groundwater (GW) or groundwater plus glucose (GW+G) to investigate the extent of As reduction in relation to iron (Fe) transformation and characterize the microbial community structure and function by sequencing 16S rRNA and arsenate dissimilatory reductase (arrA) genes. Under the carbon-limited conditions of the GW treatment, As reduction was independent of Fe reduction, despite the abundance of sequences related to Geobacter and Shewanella, genera that include a variety of dissimilatory iron-reducing bacteria. The addition of glucose, an electron donor and carbon source, caused substantial shifts toward domination of the bacterial community by Clostridium-related organisms, and As reduction was correlated with Fe reduction for the sediments from the redox transition zone. The arrA gene sequencing from microcosms at day 54 of incubation showed the presence of 14 unique phylotypes, none of which were related to any previously described arrA gene sequence, suggesting a unique community of dissimilatory arsenate-respiring bacteria in the Cache Valley Basin.
Effect of biostimulation on the microbial community in PCB-contaminated sediments through periodic amendment of sediment with iron.
Srinivasa Varadhan, A; Khodadoust, Amid P; Brenner, Richard C
Reductive dehalogenation of polychlorinated biphenyls (PCBs) by indigenous dehalorespiring microorganisms in contaminated sediments may be enhanced via biostimulation by supplying hydrogen generated through the anaerobic corrosion of elemental iron added to the sediment. In this study, the effect of periodic amendment of sediment with various dosages of iron on the microbial community present in sediment was investigated using phospholipid fatty acid analysis (PLFA) over a period of 18 months. Three PCB-contaminated sediments (two freshwater lake sediments and one marine sediment) were used. Signature biomarker analysis of the microbial community present in all three sediments revealed the enrichment of Dehalococcoides species, the population of which was sustained for a longer period of time when the sediment microcosms were amended with the lower dosage of iron (0.01 g iron per g dry sediment) every 6 months as compared to the blank system (without iron). Lower microbial stress levels were reported for the system periodically amended with 0.01 g of iron per g dry sediment every 6 months, thus reducing the competition from other hydrogen-utilizing microorganisms like methanogens, iron reducers, and sulfate reducers. The concentration of hydrogen in the system was found to be an important factor influencing the shift in microbial communities in all sediments with time. Periodic amendment of sediment with larger dosages of iron every 3 months resulted in the early prevalence of Geobacteraceae and sulfate-reducing bacteria followed by methanogens. An average pH of 8.4 (range of 8.2-8.6) and an average hydrogen concentration of 0.75% (range of 0.3-1.2%) observed between 6 and 15 months of the study were found to be conducive to sustaining the population of Dehalococcoides species in the three sediments amended with 0.01 g iron per g dry sediment. Biostimulation of indigenous PCB dechlorinators by the periodic amendment of contaminated sediments with low dosages of
Small, M.
In the search for a pure, available iron source, steelmakers are focusing their attention on Directly Reduced Iron (DRI). This material is produced by the reaction of a low gangue iron ore with a hydrocarbonaceous substance. Commercially, DRI is generated in four different reactors: shaft (moving-bed), rotary kiln, fluidized bed, and retort (fixed-bed). Annual worldwide production capacity approaches 33 million metric tons. Detailed assessments have been made of the uses of DRI, especially as a substitute for scrap in electric furnace (EF) steelmaking. DRI is generally of a quality superior to current grades of scrap, with steels produced more efficiently in the EF and containing lower levels of impurities. However, present economics favor EF steel production with scrap. But this situation could change within this decade because of a developing scarcity of good quality scrap.
Role of sulfate reduction in long term accumulation of organic and inorganic sulfur in lake sediments
International Nuclear Information System (INIS)
Rudd, J.W.M.; Kelly, C.A.; Furutani, A.
Sulfate reduction and the accumulation of reduced sulfur in epilimnetic sediments were studied in lakes in southern Norway, the Adirondack Mountains, and at the Experimental Lakes Area (ELA) of northwestern Ontario. In all of the lakes, sulfate reduction produced substantial quantities of pyrite and organic sulfur compounds. In 9-month in situ experiments at ELA using 35 S, there was a large loss (55%) with time of the S initially reduced and deposited in the sediments and a preferential loss of inorganic S compounds which led to a predominance of organic 35 S accumulation in the sediments. An intensive study of long term accumulation of sulfur in the epilimnetic sediments of four Adirondack lakes also showed that the most important long term end product of sulfate reduction was organic S and that sulfate reduction was the major source of S to the sediments. Because of high concentrations of iron in all of the sediments samples and because of the long term storage of sulfur in sediments, mostly as organic S, iron did not limit iron sulfide accumulation in these sediments. Iron limitation is unlikely to occur except in unusual circumstances. This study indicates that formation of organic S in epilimnetic sediments is primarily responsible for H + consumption via sulfate reduction in acidified lakes
Long distance electron transmission couples sulphur, iron, calcium and oxygen cycling in marine sediment
DEFF Research Database (Denmark)
Risgaard-Petersen, Nils; Nielsen, Lars Peter
sulfide oxidation leads to electric field formation, sulfide depletion and acidification of the upper centimeters of the sediment. This promoted ion migration and dissolution of carbonates and iron sulfides. Sulfide released from iron sulfides was the major e-donor in the system. Ferrous iron released...... from iron sulfides was to a large extend deposited in the oxic zone as iron oxides and Ca2+ eventually precipitates at the surface as due to high pH caused by cathodic oxygen reduction. The result show how long distance electron transmission allows oxygen to drive the allocation of important minerals...... geochemical alterations in the upper centimetres of the anoxic sediment: Sulphides were oxidized to sulphate in anoxic sediment layers. Electrons from this half-reaction were passed to the oxic layers cm above. In this way the domain of oxygen was extended far beyond it's physically presence. Bioelectrical...
Suspension Hydrogen Reduction of Iron Oxide Concentrates
Energy Technology Data Exchange (ETDEWEB)
H.Y. Sohn
The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.
The Importance of Microbial Iron Sulfide Oxidation for Nitrate Depletion in Anoxic Danish Sediments
DEFF Research Database (Denmark)
Vaclavkova, Sarka; Jacobsen, Ole Stig; Jørgensen, Christian Juncher
of organic carbon in the sediment. An apparent salinity limitation to MISON was observed in the most brackish environment. Addition of high surface area synthetically precipitated iron sulfide (FeS x ) to the aquifer sediment with the lowest natural FeS x reactivity increased both the relative fraction of NO......Nitrate (NO3 −) reduction processes are important for depleting the NO3 − load from agricultural source areas before the discharge water reaches surface waters or groundwater aquifers. In this study, we experimentally demonstrate the co-occurrence of microbial iron sulfide oxidation by NO3 − (MISON......) and other NO3 −-depleting processes in a range of contrasting sediment types: sandy groundwater aquifer, non-managed minerotrophic freshwater peat and two brackish muddy sediments. Approximately 1/3 of the net NO3 − reduction was caused by MISON in three of the four environments despite the presence...
Chemical Reduction Synthesis of Iron Aluminum Powders
Zurita-Méndez, N. N.; la Torre, G. Carbajal-De; Ballesteros-Almanza, L.; Villagómez-Galindo, M.; Sánchez-Castillo, A.; Espinosa-Medina, M. A.
In this study, a chemical reduction synthesis method of iron aluminum (FeAl) nano-dimensional intermetallic powders is described. The process has two stages: a salt reduction and solvent evaporation by a heat treatment at 1100°C. The precursors of the synthesis are ferric chloride, aluminum foil chips, a mix of Toluene/THF in a 75/25 volume relationship, and concentrated hydrochloric acid as initiator of the reaction. The reaction time was 20 days, the product obtained was dried at 60 °C for 2 h and calcined at 400, 800, and 1100 °C for 4 h each. To characterize and confirm the obtained synthesis products, X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM) techniques were used. The results of morphology and chemical characterization of nano-dimensional powders obtained showed a formation of agglomerated particles of a size range of approximately 150 nm to 1.0 μm. Composition of powders was identified as corundum (Al2O3), iron aluminide (FeAl3), and iron-aluminum oxides (Fe0. 53Al0. 47)2O3 phases. The oxide phases formation were associated with the reaction of atmospheric concentration-free oxygen during synthesis and sintering steps, reducing the concentration of the iron aluminum phase.
Shelf-to-basin iron shuttling enhances vivianite formation in deep Baltic Sea sediments
Reed, Daniel C.; Gustafsson, Bo G.; Slomp, Caroline P.
Coastal hypoxia is a growing and persistent problem largely attributable to enhanced terrestrial nutrient (i.e., nitrogen and phosphorus) loading. Recent studies suggest phosphorus removal through burial of iron (II) phosphates, putatively vivianite, plays an important role in nutrient cycling in the Baltic Sea - the world's largest anthropogenic dead zone - yet the dynamics of iron (II) phosphate formation are poorly constrained. To address this, a reactive-transport model was used to reconstruct the diagenetic and depositional history of sediments in the Fårö basin, a deep anoxic and sulphidic region of the Baltic Sea where iron (II) phosphates have been observed. Simulations demonstrate that transport of iron from shelf sediments to deep basins enhances vivianite formation while sulphide concentrations are low, but that pyrite forms preferentially over vivianite when sulphate reduction intensifies due to elevated organic loading. Episodic reoxygenation events, associated with major inflows of oxic waters, encourage the retention of iron oxyhydroxides and iron-bound phosphorus in sediments, increasing vivianite precipitation as a result. Results suggest that artificial reoxygenation of the Baltic Sea bottom waters could sequester up to 3% of the annual external phosphorus loads as iron (II) phosphates, but this is negligible when compared to potential internal phosphorus loads due to dissolution of iron oxyhydroxides when low oxygen conditions prevail. Thus, enhancing vivianite formation through artificial reoxygenation of deep waters is not a viable engineering solution to eutrophication in the Baltic Sea. Finally, simulations suggest that regions with limited sulphate reduction and hypoxic intervals, such as eutrophic estuaries, could act as important phosphorus sinks by sequestering vivianite. This could potentially alleviate eutrophication in shelf and slope environments.
Evidence for Microbial Iron Reduction in a Landfill Leachate-Polluted Aquifer (Vejen, Denmark)
DEFF Research Database (Denmark)
Albrechtsen, Hans-Jørgen; Christensen, Thomas Højlund
Aquifer sediment samples obtained from the anaerobic part of a landfill leachate plume in Vejen, Denmark, were suspended in groundwater or in an artificial medium and incubated. The strictly anaerobic suspensions were tested for reduction of ferric iron (Fe(III)) oxides, which was measured...
[Influence of Dissimilatory Iron Reduction on the Speciation and Bioavailability of Heavy Metals in Soil].
Si, You-bin; Wang, Juan
Fe(III) dissimilatory reduction by microbes is an important process of producing energy in the oxidation of organic compounds under anaerobic condition with Fe(III) as the terminal electron acceptor and Fe(II) as the reduction product. This process is of great significance in element biogeochemical cycle. Iron respiration has been described as one of the most ancient forms of microbial metabolism on the earth, which is bound up with material cycle in water, soil and sediments. Dissimilatory iron reduction plays important roles in heavy metal form transformation and the remediation of heavy metal and radionuclide contaminated soils. In this paper, we summarized the research progress of iron reduction in the natural environment, and discussed the influence and the mechanism of dissimilatory iron reduction on the speciation and bioavailability of heavy metals in soil. The effects of dissimilatory iron reduction on the speciation of heavy metals may be attributed to oxidation and reduction, methytation and immobilization of heavy metals in relation to their bioavailability in soils. The mechanisms of Fe(III) dissimilatory reduction on heavy metal form transformation contain biological and chemical interactions, but the mode of interaction remains to be further investigated.
Sulfur and Iron Cycling in a Coastal Sediment - Radiotracer Studies and Seasonal Dynamics
DEFF Research Database (Denmark)
The seasonal variation in sulfate reduction and the dynamics of sulfur and iron geochemistry were studied throughout a year in sediment of Aarhus Bay, Denmark. A radiotracer method for measuring sulfate reduction rates was applied with incubation times down to 15 min and a depth resolution down...... to 2 mm in the oxidized surface layer of the sediment. The radiotracer data were analyzed by a mathematical model which showed that, due to partial, rapid reoxidation of radioactive sulfide during incubation, the actual reduction rates in this layer were probably underestimated 5-fold. In the deeper......, sulfidic zone, measured rates appeared to be correct. Sulfate reduction followed the seasonal variation in temperature with maximum activity at 1-2 cm depth in late summer. In spite of its rapid production, free H2S was detectable in the porewater only below the depth of free Fe2+ at 6-7 cm throughout...
Uranium speciation and stability after reductive immobilization in aquifer sediments
Sharp, Jonathan O.; Lezama-Pacheco, Juan S.; Schofield, Eleanor J.; Junier, Pilar; Ulrich, Kai-Uwe; Chinni, Satya; Veeramani, Harish; Margot-Roquier, Camille; Webb, Samuel M.; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan
It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO 2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron release. Despite initial augmentation with Shewanella oneidensis, bacteria belonging to the phylum Firmicutes dominated the biostimulated columns. The immobilization of uranium (˜1 mmol U per kg sediment) enabled analysis by X-ray absorption spectroscopy (XAS). Tetravalent uranium associated with these sediments did not have spectroscopic signatures representative of U-U shells or crystalline UO 2. Analysis by microfocused XAS revealed concentrated micrometer regions of solid U(IV) that had spectroscopic signatures consistent with bulk analyses and a poor proximal correlation (μm scale resolution) between U and Fe. A plausible explanation, supported by biogeochemical conditions and spectral interpretations, is uranium association with phosphoryl moieties found in biomass; hence implicating direct enzymatic uranium reduction. After the immobilization phase, two months of in situ exposure to oxic influent did not result in substantial uranium remobilization. Ex situ flow-through experiments demonstrated more rapid uranium mobilization than observed in column oxidation studies and indicated that sediment-associated U(IV) is more mobile than biogenic UO 2. This work suggests that in situ uranium bioimmobilization studies and subsurface modeling parameters should be expanded to account for non-uraninite U(IV) species associated with biomass.
Biogeochemistry of pyrite and iron sulfide oxidation in marine sediments
DEFF Research Database (Denmark)
Schippers, A.; Jørgensen, BB
as substrates and NO3- as electron acceptor, in the presence of (FeS2)-Fe-55, to test for co-oxidation of FeS2, but an anaerobic microbial dissolution of (FeS2)-Fe-55, could not been detected. FeS2 and FeS were not oxidized by amorphous Fe(III) oxide in the presence of Fe-complexing organic compounds......Pyrite (FeS2) and iron monosulfide (FeS) play a central role in the sulfur and iron cycles of marine sediments, They may be buried in the sediment or oxidized by O-2 after transport by bioturbation to the sediment surface. FeS2 and FeS may also be oxidized within the anoxic sediment in which NO3...... marine sediments and incubated at different temperatures for > 1 yr. Bacteria could not be enriched with FeS2 as substrate or with FeS and amorphous Fe(III) oxide. With FeS and NO3-, 14 enrichments were obtained. One of these enrichments was further cultivated anaerobically with Fe2+ and S-0...
Are iron-phosphate minerals a sink for phosphorus in anoxic Black Sea sediments?
Directory of Open Access Journals (Sweden)
Nikki Dijkstra
Full Text Available Phosphorus (P is a key nutrient for marine organisms. The only long-term removal pathway for P in the marine realm is burial in sediments. Iron (Fe bound P accounts for a significant proportion of this burial at the global scale. In sediments underlying anoxic bottom waters, burial of Fe-bound P is generally assumed to be negligible because of reductive dissolution of Fe(III (oxyhydroxides and release of the associated P. However, recent work suggests that Fe-bound P is an important burial phase in euxinic (i.e. anoxic and sulfidic basin sediments in the Baltic Sea. In this study, we investigate the role of Fe-bound P as a potential sink for P in Black Sea sediments overlain by oxic and euxinic bottom waters. Sequential P extractions performed on sediments from six multicores along two shelf-to-basin transects provide evidence for the burial of Fe-bound P at all sites, including those in the euxinic deep basin. In the latter sediments, Fe-bound P accounts for more than 20% of the total sedimentary P pool. We suggest that this P is present in the form of reduced Fe-P minerals. We hypothesize that these minerals may be formed as inclusions in sulfur-disproportionating Deltaproteobacteria. Further research is required to elucidate the exact mineral form and formation mechanism of this P burial phase, as well as its role as a sink for P in sulfide-rich marine sediments.
Are iron-phosphate minerals a sink for phosphorus in anoxic Black Sea sediments?
Dijkstra, Nikki; Kraal, Peter; Kuypers, Marcel M M; Schnetger, Bernhard; Slomp, Caroline P
Phosphorus (P) is a key nutrient for marine organisms. The only long-term removal pathway for P in the marine realm is burial in sediments. Iron (Fe) bound P accounts for a significant proportion of this burial at the global scale. In sediments underlying anoxic bottom waters, burial of Fe-bound P is generally assumed to be negligible because of reductive dissolution of Fe(III) (oxyhydr)oxides and release of the associated P. However, recent work suggests that Fe-bound P is an important burial phase in euxinic (i.e. anoxic and sulfidic) basin sediments in the Baltic Sea. In this study, we investigate the role of Fe-bound P as a potential sink for P in Black Sea sediments overlain by oxic and euxinic bottom waters. Sequential P extractions performed on sediments from six multicores along two shelf-to-basin transects provide evidence for the burial of Fe-bound P at all sites, including those in the euxinic deep basin. In the latter sediments, Fe-bound P accounts for more than 20% of the total sedimentary P pool. We suggest that this P is present in the form of reduced Fe-P minerals. We hypothesize that these minerals may be formed as inclusions in sulfur-disproportionating Deltaproteobacteria. Further research is required to elucidate the exact mineral form and formation mechanism of this P burial phase, as well as its role as a sink for P in sulfide-rich marine sediments.
The role of microbial iron reduction in the formation of Proterozoic molar tooth structures
Hodgskiss, Malcolm S. W.; Kunzmann, Marcus; Poirier, André; Halverson, Galen P.
Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600-720 Ma, but do not occur in rocks older or younger, with the exception of two isolated Ediacaran occurrences. Despite being locally volumetrically significant in carbonate rocks of this age, their formation and disappearance in the geological record remain enigmatic. Here we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and sulphur contents for 87 samples from units in ten different basins spanning ca. 1900-635 Ma. The iron isotope composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or residue components in the host sediment. We interpret the isotopically light iron in molar tooth structures to have been produced by dissimilatory iron reduction utilising Fe-rich smectites and Fe-oxyhydroxides in the upper sediment column. The microbial conversion of smectite to illite results in a volume reduction of clay minerals (∼30%) while simultaneously increasing pore water alkalinity. When coupled with wave loading, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures in the mid-Neoproterozoic is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and an increase in the concentration of O2 in shallow seawater.
Vertical activity distribution of dissimilatory nitrate reduction in coastal marine sediments
DEFF Research Database (Denmark)
Behrendt, A.; de Beer, D.; Stief, P.
The relative importance of two dissimilatory nitrate reduction pathways, denitrification (DEN) and dissimilatory nitrate reduction to ammonium (DNRA), was investigated in intact sediment cores from five different coastal marine field sites (Dorum, Aarhus Bight, Mississippi Delta, Limfjord...... reduction was clearly dominated by DEN (59-131% of the total NO3- reduced) rather than by DNRA, irrespective of the sedimentary inventories of electron donors such as organic carbon, sulfide, and iron. Highest ammonium production via DNRA, accounting for up to 8.9% of the total NO3- reduced, was found...... was detected accounting for 37-77% of the total NO3- reduced. These contradictory results might be explained by enhanced NO3- availability for DNRA bacteria in the sediment slurries compared to the core-incubated sediments in which diffusion of NO3- from the water column may only reach DEN bacteria...
Reduction experiment of iron scale by adding waste plastics.
Zhang, Chongmin; Chen, Shuwen; Miao, Xincheng; Yuan, Hao
The special features of waste plastics in China are huge in total amount, various in type and dispersive in deposition. Therefore, it is necessary to try some new ways that are fit to Chinese situation for disposing waste plastics as metallurgical raw materials more effectively and flexibly. Owing to its high ferrous content and less impurity, the iron scale became ideal raw material to produce pure iron powder. One of the methods to produce pure iron powder is Hoganas Method, by which, after one or multistage of reduction steps, the iron scale can be reduced pure iron powder. However, combining utilization of waste plastics and iron powder production, a series of reduction experiments were arranged and investigated, which is hoped to take use of both thermal and chemical energy contained in waste plastics as well as to improve the reducing condition of iron scale, and hence to develop a new metallurgical way of disposing waste plastics. The results show that under these experimental conditions, the thermal-decomposition of water plastics can conduce to an increase of porosity in the reduction systems. Moreover, better thermodynamics and kinetics conditions for the reduction of scale can be reached. As a result, the reduction rate is increased.
Continuous Strip Reduction Test Simulating Tribological Conditions in Ironing
DEFF Research Database (Denmark)
Üstünyagiz, Esmeray; Nielsen, Chris Valentin; Christiansen, Peter
materials, surface roughnesses, normal pressure, sliding length, sliding speed, interface temperature and lubrication. This paper proposes a new Strip Reduction Test (SRT) for industrial ironing processes that is capable of replicating the highly severe tribological conditions that are experienced during...
Manganese and iron as oxygen carriers to anoxie estuarine sediment
Brayner, F. M. M.; Matvienko, B.
We studied the concentration of a series of transition metals including Mn and Fe in an estuarine fishpond. The pond is situated at latitude 8°10'S and longitude 34°55'W, in the Capibaribe River estuary, within the Recife city boundaries, which is located in Pernambuco, a state of the Brazilian Northeast Pond area is 1.5 ha and it bas a 0.5 m depth. It is separated from the river by dikes. Water temperature at 28° C is stable throughout the year. Light breezes keep the water aerated, but intense ongoing decomposition makes the sediment anoxie. The area, originally of mangrove type, has been changed by antropic action on its fauna and vegetation. The study focuses on changes in behaviour of heavy metals. Samples of bottom sediments wore collected by Eckman dredge sediment sampler and total metal concentration was determined by the lithium borate fusion method. Water, recent sediment, and consolidated sediment were examined in this fishpond where Mn and Fe are brought in periodically by water and then gradually go into the sediment at respective rates of 10.52 and 1332 mg m^{-2}a^{-1}. Strong bioturbation re-suspends sediment while simultaneously re-dissolution of these ions is going on fhrough reduction in the anoxie sédiment. As soluble species these ions migrate from sediment to water and are there continually oxidized by dissolved oxygen, becoming insoluble. With their precipitation, chemically bound oxygen is carried down to the sediment, constituting a parallel channel of transport in addition to migration into the sediment bydiffusion of the oxygen dissolved in the water. The estimated flow rates are 3.25 and 76 mg O2 m^{-2}a^{-1} due to Mn and Fe respectively. The rates were established using natural silicon as a tracer.
Anaerobic carbon mineralisation through sulphate reduction in the inner shelf sediments of eastern Arabian sea
Digital Repository Service at National Institute of Oceanography (India)
Naik, R.; Naqvi, S.W.A.; Araujo, J.
,G.-J. .Reichart and S. W. Poulton. 2012. Sedimentary phosphorus and iron cycling in and below the oxygen minimum zone of the northern Arabian Sea.Biogeosciences Discussion. 9, 3829–3880. Pratihary A.K, S. W. A. Naqvi, H. Naik,B.R. Thorat, G. Narvenkar...). Other factors such as sedimentation rate and the presence of anaerobic electron acceptors asnitrate, Fe and Mn oxyhydroxides also affect sedimentary Corg mineralization rates.Under anoxic conditions, reductive dissolution of Fe oxyhyroxides produces...
Concentration-dependent sedimentation properties of ferritin: implications for estimation of iron contents of serum ferritins
International Nuclear Information System (INIS)
Niitsu, Y.; Adachi, C.; Takahashi, F.; Goto, Y.; Kohgo, Y.; Urushizaki, I.; Listowsky, I.
Serum ferritins from various sources sedimented at lower densities than tissue ferritins in sucrose gradient centrifugation systems. The sedimentation patterns of ferritins, however, were shown to be dependent on the concentration of the protein; as the concentration decreased the protein appeared to sediment at lower densities. Thus, at the low concentration levels usually used for analysis of serum ferritin, tissue ferritins also sedimented in the same lower density regions. Iron labeling experiments indicated that the sedimentation changes upon dilution were not due to release of iron or was there any indication that the protein dissociated into subunits. The anomalous sedimentation behavior of serum ferritin should therefore not be interpreted in terms of its iron content. The disclosure that serum ferritins may have full complements of iron is counter to the prevalent view that serum ferritins are low iron forms and has potential implications with regard to the sources and possible function of this protein in the circulation
Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.
Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi
Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in
Reductive Dechlorination of Polychlorinated Biphenyls in Marine Sediments
National Research Council Canada - National Science Library
Sowers, Kevin
... Community by Comparative Sequence Analysis of Genes Coding for 16S rRNA, Microbial Reductive Dechlorination of Aroclor 1260 in Anaerobic Slurries of Estuarine Sediments, Differential RFLP patterns of PCR...
Dolochar as a reductant in the reduction roasting of iron ore slimes
Rath, Swagat S.; Rao, Danda Srinivas
The present investigation examines the viability of dolochar, a sponge iron industry waste material, as a reductant in the reduction roasting of iron ore slimes, which are another waste generated by iron ore beneficiation plants. Under statistically determined optimum conditions, which include a temperature of 900°C, a reductant-to-feed mass ratio of 0.35, and a reduction time of 30-45 min, the roasted mass, after being subjected to low-intensity magnetic separation, yielded an iron ore concentrate of approximately 64wt% Fe at a mass recovery of approximately 71% from the feed iron ore slime assaying 56.2wt% Fe. X-ray diffraction analyses indicated that the magnetic products contain magnetite and hematite as the major phases, whereas the nonmagnetic fractions contain quartz and hematite.
Application Of Bacterial Iron Reduction For The Removal Of Iron Impurities From Industrial Silica Sand And Kaolin
Zegeye, A.; Yahaya, S.; Fialips, C. I.; White, M.; Manning, D. A.; Gray, N.
Biogeochemical evidence exists to support the potential importance of crystalline or amorphous Fe minerals as electron acceptor for Fe reducing bacteria in soils and subsurface sediments. This microbial metabolic activity can be exploited as alternative method in different industrial applications. For instance, the removal of ferric iron impurities from minerals for the glass and paper industries currently rely on physical and chemical treatments having substantial economical and environmental disadvantages. The ability to remove iron by other means, such as bacterial iron reduction, may reduce costs, allow lower grade material to be mined, and improve the efficiency of mineral processing. Kaolin clay and silica sand are used in a wide range of industrial applications, particularly in paper, ceramics and glass manufacturing. Depending on the geological conditions of deposition, they are often associated with iron (hydr)oxides that are either adsorbed to the mineral surfaces or admixed as separate iron bearing minerals. In this study, we have examined the Fe(III) removal efficiency from kaolin and silica sand by a series of iron- reducing bacteria from the Shewanella species (S. alga BrY, S. oneidensis MR-1, S. putrefaciens CN32 and S. putrefaciens ATCC 8071) in the presence of anthraquinone 2,6 disulfonate (AQDS). We have also investigated the effectiveness of a natural organic matter, extracted with the silica sand, as a substitute to AQDS for enhancing Fe(III) reduction kinetics. The microbial reduction of Fe(III) was achieved using batch cultures under non-growth conditions. The rate and the extent of Fe(III) reduction was monitored as a function of the initial Fe(III) content, Shewanella species and temperature. The bacterially- treated minerals were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD) to observe any textural and mineralogical transformation. The whiteness and ISO brightness of the kaolin was also measured by
Ferric Iron Reduction by Bacteria Associated with the Roots of Freshwater and Marine Macrophytes†
King, G. M.; Garey, Meredith A.
In vitro assays of washed, excised roots revealed maximum potential ferric iron reduction rates of >100 μmol g (dry weight)−1 day−1 for three freshwater macrophytes and rates between 15 and 83 μmol (dry weight)−1 day−1 for two marine species. The rates varied with root morphology but not consistently (fine root activity exceeded smooth root activity in some but not all cases). Sodium molybdate added at final concentrations of 0.2 to 20 mM did not inhibit iron reduction by roots of marine macrophytes (Spartina alterniflora and Zostera marina). Roots of a freshwater macrophyte, Sparganium eurycarpum, that were incubated with an analog of humic acid precursors, anthroquinone disulfate (AQDS), reduced freshly precipitated iron oxyhydroxide contained in dialysis bags that excluded solutes with molecular weights of >1,000; no reduction occurred in the absence of AQDS. Bacterial enrichment cultures and isolates from freshwater and marine roots used a variety of carbon and energy sources (e.g., acetate, ethanol, succinate, toluene, and yeast extract) and ferric oxyhydroxide, ferric citrate, uranate, and AQDS as terminal electron acceptors. The temperature optima for a freshwater isolate and a marine isolate were equivalent (approximately 32°C). However, iron reduction by the freshwater isolate decreased with increasing salinity, while reduction by the marine isolate displayed a relatively broad optimum salinity between 20 and 35 ppt. Our results suggest that by participating in an active iron cycle and perhaps by reducing humic acids, iron reducers in the rhizoplane of aquatic macrophytes limit organic availability to other heterotrophs (including methanogens) in the rhizosphere and bulk sediments. PMID:10508065
Microbiological reduction of Sb(V) in anoxic freshwater sediments
Oremland, Ronald S.; Kulp, Thomas R.; Miller, Laurence G.; Braiotta, Franco; Webb, Samuel M.; Kocar, Benjamin D; Blum, Jodi S.
Microbiological reduction of millimolar concentrations of Sb(V) to Sb(III) was observed in anoxic sediments from two freshwater settings: (1) a Sb- and As-contaminated mine site (Stibnite Mine) in central Idaho and 2) an uncontaminated suburban lake (Searsville Lake) in the San Francisco Bay Area. Rates of Sb(V) reduction in anoxic sediment microcosms and enrichment cultures were enhanced by amendment with lactate or acetate as electron donors but not by H2, and no reduction occurred in sterilized controls. Addition of 2-14C-acetate to Stibnite Mine microcosms resulted in the production of 14CO2 coupled to Sb(V) reduction, suggesting that this process proceeds by a dissimilatory respiratory pathway in those sediments. Antimony(V) reduction in Searsville Lake sediments was not coupled to acetate mineralization and may be associated with Sb-resistance. The microcosms and enrichment cultures also reduced sulfate, and the precipitation of insoluble Sb(III)-sulfide complexes was a major sink for reduced Sb. The reduction of Sb(V) by Stibnite Mine sediments was inhibited by As(V), suggesting that As(V) is a preferred electron acceptor for the indigenous community. These findings indicate a novel pathway for anaerobic microbiological respiration and suggest that communities capable of reducing high concentrations of Sb(V) commonly occur naturally in the environment.
Uranium speciation and stability after reductive immobilization in sediments.
Sharp J.O
It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO2). In order to explore the form and stability of uranium immobilized under these conditions we introduced lactate (15 mM for 3 months) into flow through columns containing sediments derived from a former uranium processing site at Old Rifle CO. This resulted in metal reducing conditions as evidenced by concurrent uranium uptake and iron re...
Uranium speciation and stability after reductive immobilization in sediments
Sharp, Jonathan O.; Schofield, Eleanor J.; Lezama-Pacheco, Juan S.; Webb, Sam; Ulrich, Kai-Uwe; Blue, Lisa; Chinni, Satyavani; Veeramani, Harish; Junier, Pilar; Margot-Roquier, Camille; Suvorova Buffat, Elena; Tebo, Bradley M.; Giammar, Daniel E.; Bargar, John R.; Bernier-Latmani, Rizlan
It has generally been assumed that the bioreduction of hexavalent uranium in groundwater systems will result in the precipitation of immobile uraninite (UO2). In order to explore the form and stability of uranium immobilized under these conditions, we introduced lactate (15 mM for 3 months) into flow-through columns containing sediments derived from a former uranium-processing site at Old Rifle, CO. This resulted in metal-reducing conditions as evidenced by concurrent uranium uptake and iron ...
Reductive precipitation of neptunium on iron surfaces under anaerobic conditions
Yang, H.; Cui, D.; Grolimund, D.; Rondinella, V. V.; Brütsch, R.; Amme, M.; Kutahyali, C.; Wiss, A. T.; Puranen, A.; Spahiu, K.
Reductive precipitation of the radiotoxic nuclide 237Np from nuclear waste on the surface of iron canister material at simulated deep repository conditions was investigated. Pristine polished as well as pre-corroded iron specimens were interacted in a deoxygenated solution containing 10-100 μM Np(V), with 10 mM NaCl and 2 mM NaHCO3 as background electrolytes. The reactivity of each of the two different systems was investigated by analyzing the temporal evolution of the Np concentration in the reservoir. It was observed that pre-oxidized iron specimen with a 40 μm Fe3O4 corrosion layer are considerably more reactive regarding the reduction and immobilization of aqueous Np(V) as compared to pristine polished Fe(0) surfaces. 237Np immobilized by the reactive iron surfaces was characterized by scanning electron microscopy as well as synchrotron-based micro-X-ray fluorescence and X-ray absorption spectroscopy. At the end of experiments, a 5-8 μm thick Np-rich layer was observed to be formed ontop of the Fe3O4 corrosion layer on the iron specimen. The findings from this work are significant in the context of performance assessments of deep geologic repositories using iron as high level radioactive waste (HLW) canister material and are of relevance regarding removing pollutants from contaminated soil or groundwater aquifer systems.
Preliminary characterization and biological reduction of putative biogenic iron oxides (BIOS) from the Tonga-Kermadec Arc, southwest Pacific Ocean.
Langley, S; Igric, P; Takahashi, Y; Sakai, Y; Fortin, D; Hannington, M D; Schwarz-Schampera, U
Sediment samples were obtained from areas of diffuse hydrothermal venting along the seabed in the Tonga sector of the Tonga-Kermadec Arc, southwest Pacific Ocean. Sediments from Volcano 1 and Volcano 19 were analyzed by X-ray diffraction (XRD) and found to be composed primarily of the iron oxyhydroxide mineral, two-line ferrihydrite. XRD also suggested the possible presence of minor amounts of more ordered iron (hydr)oxides (including six-line ferrihydrite, goethite/lepidocrocite and magnetite) in the biogenic iron oxides (BIOS) from Volcano 1; however, Mössbauer spectroscopy failed to detect any mineral phases more crystalline than two-line ferrihydrite. The minerals were precipitated on the surfaces of abundant filamentous microbial structures. Morphologically, some of these structures were similar in appearance to the known iron-oxidizing genus Mariprofundus spp., suggesting that the sediments are composed of biogenic iron oxides. At Volcano 19, an areally extensive, active vent field, the microbial cells appeared to be responsible for the formation of cohesive chimney-like structures of iron oxyhydroxide, 2-3 m in height, whereas at Volcano 1, an older vent field, no chimney-like structures were apparent. Iron reduction of the sediment material (i.e. BIOS) by Shewanella putrefaciens CN32 was measured, in vitro, as the ratio of [total Fe(II)]:[total Fe]. From this parameter, reduction rates were calculated for Volcano 1 BIOS (0.0521 day(-1)), Volcano 19 BIOS (0.0473 day(-1)), and hydrous ferric oxide, a synthetic two-line ferrihydrite (0.0224 day(-1)). Sediments from both BIOS sites were more easily reduced than synthetic ferrihydrite, which suggests that the decrease in effective surface area of the minerals within the sediments (due to the presence of the organic component) does not inhibit subsequent microbial reduction. These results indicate that natural, marine BIOS are easily reduced in the presence of dissimilatory iron-reducing bacteria, and that the
Mercury methylation coupled to iron reduction by dissimilatory iron-reducing bacteria.
Si, Youbin; Zou, Yan; Liu, Xiaohong; Si, Xiongyuan; Mao, Jingdong
Iron reduction and mercury methylation by dissimilatory iron-reducing bacteria (DIRB), Geobacter sulfurreducens and Shewanella oneidensis, were studied, and the relationship of mercury methylation coupled to iron reduction was determined. The ability of both bacteria for reducing iron was tested, and Fe(III) reduction occurred with the highest rate when ferric oxyhydroxide was used as a terminal electron acceptor. G. sulfurreducens had proven to mediate the production of methylmercury (MeHg), and a notable increase of MeHg following the addition of inorganic Hg was observed. When the initial concentration of HgCl2 was 500nM, about 177.03nM of MeHg was determined at 8d after G. sulfurreducens inoculation. S. oneidensis was tested negligible for Hg methylation and only 12.06nM of MeHg was determined. Iron reduction could potentially influence Hg methylation rates. The increase in MeHg was consistent with high rate of iron reduction, indicating that Fe(III) reduction stimulated the formation of MeHg. Furthermore, the net MeHg concentration increased at low Fe(III) additions from 1.78 to 3.57mM, and then decreased when the added Fe(III) was high from 7.14 to 17.85mM. The mercury methylation rate was suppressed with high Fe(III) additions, which might have been attributable to mercury complexation and low availability. Copyright © 2014 Elsevier Ltd. All rights reserved.
The Evolution of Sulfide in Shallow Aquatic Ecosystem Sediments: An Analysis of the Roles of Sulfate, Organic Carbon, and Iron and Feedback Constraints Using Structural Equation Modeling
Pollman, C. D.; Swain, E. B.; Bael, D.; Myrbo, A.; Monson, P.; Shore, M. D.
The generation of elevated concentrations of sulfide in sediment pore waters that are toxic to rooted macrophytes is problematic in both marine and freshwaters. In marine waters, biogeochemical conditions that lead to toxic levels of sulfide generally relate to factors that affect oxygen dynamics or the sediment iron concentration. In freshwaters, increases in surface water sulfate have been implicated in decline of Zizania palustris (wild rice), which is important in wetlands across the Great Lakes region of North America. We developed a structural equation (SE) model to elucidate key variables that govern the evolution of sulfide in pore waters in shallow aquatic habitats that are potentially capable of supporting wild rice. The conceptual basis for the model is the hypothesis that dissimilatory sulfate reduction is limited by the availability of both sulfate and total organic carbon (TOC) in the sediment. The conceptual model also assumes that pore water sulfide concentrations are constrained by the availability of pore water iron and that sediment iron supports the supply of dissolved iron to the pore water. A key result from the SE model is that variations in three external variables (sulfate, sediment TOC, and sediment iron) contribute nearly equally to the observed variations in pore water sulfide. As a result, management efforts to mitigate against the toxic effects of pore water sulfide on macrophytes such as wild rice should approach defining a protective sulfate threshold as an exercise tailored to the geochemistry of each site that quantitatively considers the effects of ambient concentrations of sediment Fe and TOC.
Microbial reduction of uranium(VI) in sediments of different lithologies collected from Sellafield
International Nuclear Information System (INIS)
Newsome, Laura; Morris, Katherine; Trivedi, Divyesh; Atherton, Nick; Lloyd, Jonathan R.
Highlights: • U(VI) (aq) mobility can be controlled by stimulating biogeochemical interactions. • Indigenous microbes in varied sediments reduced U(VI) to insoluble U(IV). • Sediment cell numbers and amount of bioavailable Fe(III) could limit this process. - Abstract: The presence of uranium in groundwater at nuclear sites can be controlled by microbial processes. Here we describe the results from stimulating microbial reduction of U(VI) in sediment samples obtained from a nuclear-licensed site in the UK. A variety of different lithology sediments were selected to represent the heterogeneity of the subsurface at a site underlain by glacial outwash deposits and sandstone. The natural sediment microbial communities were stimulated via the addition of an acetate/lactate electron donor mix and were monitored for changes in geochemistry and molecular ecology. Most sediments facilitated the removal of 12 ppm U(VI) during the onset of Fe(III)-reducing conditions; this was reflected by an increase in the proportion of known Fe(III)- and U(VI)-reducing species. However U(VI) remained in solution in two sediments and Fe(III)-reducing conditions did not develop. Sequential extractions, addition of an Fe(III)-enrichment culture and most probable number enumerations revealed that a lack of bioavailable iron or low cell numbers of Fe(III)-reducing bacteria may be responsible. These results highlight the potential for stimulation of microbial U(VI)-reduction to be used as a bioremediation strategy at UK nuclear sites, and they emphasise the importance of both site-specific and borehole-specific investigations to be completed prior to implementation
Impacts of flocculation on the distribution and diagenesis of iron in boreal estuarine sediments
Directory of Open Access Journals (Sweden)
T. Jilbert
Full Text Available Iron (Fe plays a key role in sedimentary diagenetic processes in coastal systems, participating in various redox reactions and influencing the burial of organic carbon. Large amounts of Fe enter the marine environment from boreal river catchments associated with dissolved organic matter (DOM and as colloidal Fe oxyhydroxides, principally ferrihydrite. However, the fate of this Fe pool in estuarine sediments has not been extensively studied. Here we show that flocculation processes along a salinity gradient in an estuary of the northern Baltic Sea efficiently transfer Fe and OM from the dissolved phase into particulate material that accumulates in the sediments. Flocculation of Fe and OM is partially decoupled. This is likely due to the presence of discrete colloidal ferrihydrite in the freshwater Fe pool, which responds differently from DOM to estuarine mixing. Further decoupling of Fe from OM occurs during sedimentation. While we observe a clear decline with distance offshore in the proportion of terrestrial material in the sedimentary particulate organic matter (POM pool, the distribution of flocculated Fe in sediments is modulated by focusing effects. Labile Fe phases are most abundant at a deep site in the inner basin of the estuary, consistent with input from flocculation and subsequent focusing. The majority of the labile Fe pool is present as Fe (II, including both acid-volatile sulfur (AVS-bound Fe and unsulfidized phases. The ubiquitous presence of unsulfidized Fe (II throughout the sediment column suggests Fe (II-OM complexes derived from reduction of flocculated Fe (III-OM, while other Fe (II phases are likely derived from the reduction of flocculated ferrihydrite. Depth-integrated rates of Fe (II accumulation (AVS-Fe + unsulfidized Fe (II + pyrite for the period 1970–2015 are greater in the inner basin of the estuary with respect to a site further offshore, confirming higher rates of Fe reduction in near-shore areas
Impacts of flocculation on the distribution and diagenesis of iron in boreal estuarine sediments
Jilbert, Tom; Asmala, Eero; Schröder, Christian; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Virtasalo, Joonas J.; Kotilainen, Aarno; Peltola, Pasi; Ekholm, Päivi; Hietanen, Susanna
Iron (Fe) plays a key role in sedimentary diagenetic processes in coastal systems, participating in various redox reactions and influencing the burial of organic carbon. Large amounts of Fe enter the marine environment from boreal river catchments associated with dissolved organic matter (DOM) and as colloidal Fe oxyhydroxides, principally ferrihydrite. However, the fate of this Fe pool in estuarine sediments has not been extensively studied. Here we show that flocculation processes along a salinity gradient in an estuary of the northern Baltic Sea efficiently transfer Fe and OM from the dissolved phase into particulate material that accumulates in the sediments. Flocculation of Fe and OM is partially decoupled. This is likely due to the presence of discrete colloidal ferrihydrite in the freshwater Fe pool, which responds differently from DOM to estuarine mixing. Further decoupling of Fe from OM occurs during sedimentation. While we observe a clear decline with distance offshore in the proportion of terrestrial material in the sedimentary particulate organic matter (POM) pool, the distribution of flocculated Fe in sediments is modulated by focusing effects. Labile Fe phases are most abundant at a deep site in the inner basin of the estuary, consistent with input from flocculation and subsequent focusing. The majority of the labile Fe pool is present as Fe (II), including both acid-volatile sulfur (AVS)-bound Fe and unsulfidized phases. The ubiquitous presence of unsulfidized Fe (II) throughout the sediment column suggests Fe (II)-OM complexes derived from reduction of flocculated Fe (III)-OM, while other Fe (II) phases are likely derived from the reduction of flocculated ferrihydrite. Depth-integrated rates of Fe (II) accumulation (AVS-Fe + unsulfidized Fe (II) + pyrite) for the period 1970-2015 are greater in the inner basin of the estuary with respect to a site further offshore, confirming higher rates of Fe reduction in near-shore areas. Mössbauer 57Fe
Biostimulation of Iron Reduction and Uranium Immobilization: Microbial and Mineralogical Controls
International Nuclear Information System (INIS)
Joel E. Kostka; Lainie Petrie; Nadia North; David L. Balkwill; Joseph W. Stucki; Lee Kerkhof
The overall objective of our project is to understand the microbial and geochemical mechanisms controlling the reduction and immobilization of U(VI) during biostimulation in subsurface sediments of the Field Research Center (FRC) which are cocontaminated with uranium and nitrate. The focus will be on activity of microbial populations (metal- and nitrate-reducing bacteria) and iron minerals which are likely to make strong contributions to the fate of uranium during in situ bioremediation. The project will: (1) quantify the relationships between active members of the microbial communities, iron mineralogy, and nitrogen transformations in the field and in laboratory incubations under a variety of biostimulation conditions, (2) purify and physiologically characterize new model metal-reducing bacteria isolated from moderately acidophilic FRC subsurface sediments, and (3) elucidate the biotic and abiotic mechanisms by which FRC aluminosilicate clay minerals are reduced and dissolved under environmental conditions resembling those during biostimulation. Active microbial communities will be assessed using quantitative molecular techniques along with geochemical measurements to determine the different terminal-electron-accepting pathways. Iron minerals will be characterized using a suite of physical, spectroscopic, and wet chemical methods. Monitoring the activity and composition of the denitrifier community in parallel with denitrification intermediates during nitrate removal will provide a better understanding of the indirect effects of nitrate reduction on uranium speciation. Through quantification of the activity of specific microbial populations and an in-depth characterization of Fe minerals likely to catalyze U sorption/precipitation, we will provide important inputs for reaction-based biogeochemical models which will provide the basis for development of in situ U bioremediation strategies. In collaboration with Jack Istok and Lee Krumholz, we have begun to study the
Final report - Reduction of mercury in saturated subsurface sediments and its potential to mobilize mercury in its elemental form
Energy Technology Data Exchange (ETDEWEB)
Bakray, Tamar [Rutgers University
The goal of our project was to investigate Hg(II) reduction in the deep subsurface. We focused on microbial and abiotic pathways of reduction and explored how it affected the toxicity and mobility of Hg in this unique environment. The project's tasks included: 1. Examining the role of mer activities in the reduction of Hg(II) in denitrifying enrichment cultures; 2. Investigating the biotic/abiotic reduction of Hg(II) under iron reducing conditions; 3. Examining Hg(II) redox transformations under anaerobic conditions in subsurface sediments from DOE sites.
Structure and activity of lacustrine sediment bacteria involved in nutrient and iron cycles
DEFF Research Database (Denmark)
da Silva Martins, Gilberto Jorge; Terada, Akihiko; Ribeiro, Daniel C
Knowledge of the bacterial community structure in sediments is essential to better design restoration strategies for eutrophied lakes. In this regard, the aim of this study was to quantify the abundance and activity of bacteria involved in nutrient and iron cycling in sediments from four Azorean...
Bacterial reduction of selenium in coal mine tailings pond sediment
Energy Technology Data Exchange (ETDEWEB)
Siddique, T.; Arocena, J.M.; Thring, R.W.; Zhang, Y.Q. [University of North British Columbia, Prince George, BC (Canada)
Sediment from a storage facility for coal tailings solids was assessed for its capacity to reduce selenium (Se) by native bacterial community. One Se{sup 6+}-reducing bacterium Enterobacter hormaechei (Tar11) and four Se{sup 4+}-reducing bacteria, Klebsiella pneumoniae (Tar1), Pseudomonasfluorescens (Tar3), Stenotrophomonas maltophilia (Tar6), and Enterobacter amnigenus (Tar8) were isolated from the sediment. Enterobacter horinaechei removed 96% of the added Se{sup 6+} (0.92 mg L{sup -1} from the effluents when Se6+ was determined after 5 d of incubation. Analysis of the red precipitates showed that Se{sup 6+} reduction resulted in the formation of spherical particles ({lt}1.0 {mu} m) of Se 0 as observed under scanning electron microscope (SEM) and confirmed by EDAX. Selenium speciation was performed to examine the fate of the added Se{sup 6+} in the sediment with or without addition of Enterobacter hormaechei cells. More than 99% of the added Se{sup 6+} (about 2.5 mg L{sup -1}) was transformed in the nonsterilized sediment (without Enterobacter hormaechei cells) as well as in the sterilized (heat-killed) sediment (with Enterobacter hormaechei cells). The results of this study suggest that the lagoon sediments at the mine site harbor Se{sup 6+}- and Se{sup 4+} -reducing bacteria and may be important sinks for soluble Se (Se{sup 6+} and Se{sup 4+}). Enterobacter hormaechei isolated from metal-contaminated sediment may have potential application in removing Se from industrial effluents.
Biological reduction of iron to the elemental state from ochre deposits of Skelton Beck in Northeast England
Directory of Open Access Journals (Sweden)
Pattanathu K S M Rahman
Full Text Available Ochre, consequence of acid mine drainage, is iron oxides-rich soil pigments that can be found in the water drainage from historic base metal and coal mines. The anaerobic strains of Geobacter sulfurreducens and Shewanella denitrificans were used for the microbial reduction of iron from samples of ochre collected from Skelton Beck (Saltburn Orange River, NZ 66738 21588 in Northeast England. The aim of the research was to determine the ability of the two anaerobic bacteria to reduce the iron present in ochre and to determine the rate of the reduction process. The physico-chemical changes in the ochre sample after the microbial reduction process were observed by the production of zero-valent iron which was later confirmed by the detection of elemental Fe in XRD spectrum. The XRF results revealed that 69.16% and 84.82% of iron oxide can be reduced using G. sulfurreducens and S. denitrificans respectively after 8 days of incubation. These results could provide the basis for the development of a biohydrometallurgical process for the production of elemental iron from ochre sediments.
Removal of iron and manganese from groundwater: a study of using potassium permanganate and sedimentation
Directory of Open Access Journals (Sweden)
Elsheikh Mohamed
Full Text Available Experiments are done for different combinations of Fe+2 and Mn+2 concentrations. The obtained results show that Potassium Permanganate (PP gives good results in iron and manganese removal. By using PP dose near to half of the theoretically required one, it can remove up to 100 % and 90 % of iron and manganese, respectively over different tested concentrations at pH=7.0. Increasing rate of filtration influences the Mn+2 removal process obviously. Sedimentation is required when combined concentrations of iron and manganese are greater than 5.0 ppm to reduce filter rapid clogging. Using conventional treatment with adding alum, flocculation, sedimentation and filtration can remove up to 97% and 18% of iron and manganese, respectively. Using PP in addition to alum enhances manganese removal but decreases iron removal. However, using alum with increasing pH to 10 leads to 100 % and 95 % of Fe+2 and Mn+2 removal and increases filter working period.
Landscape planning for agricultural nonpoint source pollution reduction III: Assessing phosphorus and sediment reduction potential
Diebel, M.W.; Maxted, J.T.; Robertson, Dale M.; Han, S.; Vander Zanden, M. J.
Riparian buffers have the potential to improve stream water quality in agricultural landscapes. This potential may vary in response to landscape characteristics such as soils, topography, land use, and human activities, including legacies of historical land management. We built a predictive model to estimate the sediment and phosphorus load reduction that should be achievable following the implementation of riparian buffers; then we estimated load reduction potential for a set of 1598 watersheds (average 54 km2) in Wisconsin. Our results indicate that land cover is generally the most important driver of constituent loads in Wisconsin streams, but its influence varies among pollutants and according to the scale at which it is measured. Physiographic (drainage density) variation also influenced sediment and phosphorus loads. The effect of historical land use on present-day channel erosion and variation in soil texture are the most important sources of phosphorus and sediment that riparian buffers cannot attenuate. However, in most watersheds, a large proportion (approximately 70%) of these pollutants can be eliminated from streams with buffers. Cumulative frequency distributions of load reduction potential indicate that targeting pollution reduction in the highest 10% of Wisconsin watersheds would reduce total phosphorus and sediment loads in the entire state by approximately 20%. These results support our approach of geographically targeting nonpoint source pollution reduction at multiple scales, including the watershed scale. ?? 2008 Springer Science+Business Media, LLC.
Kinetics of chromium (VI) reduction by ferrous iron
International Nuclear Information System (INIS)
Batchelor, B.; Schlautman, M.; Hwang, I.; Wang, R.
Chromium is a primary inorganic contaminant of concern at the Pantex Plant. Chromium concentrations have been found to be two orders of magnitude higher than the drinking water standards, particularly in certain wells in the perched aquifer below Zone 12. In situ reduction of a mobile form of chromium, Cr(VI) to an immobile form, Cr(III), was examined as a viable option to active soil restoration. Successfully immobilizing chromium in the vadose zone as Cr(III) will reduce the amount of chromium that reaches the groundwater table. The results from the solution experiments indicated that chromium was rapidly and stoichiometrically reduced by Fe(II) in solution. Also, the slurry experiments showed that the aquifer solids removed Fe(II) from solution, but a portion of the iron removed remained available for reaction with Cr(VI), but at a slower rate. A model to predict different amounts of iron pseudo-components was developed, which allowed prediction of iron amounts required to reduce chromium under in situ conditions
Nitrous oxide production kinetics during nitrate reduction in river sediments.
Laverman, Anniet M; Garnier, Josette A; Mounier, Emmanuelle M; Roose-Amsaleg, Céline L
A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R(m)) ranged between 3.0 and 7.1microg Ng(-1)h(-1), and affinity constant (K(m)) ranged from 7.4 to 30.7mg N-NO(3)(-)L(-1). These values were higher in slurry incubations with an R(m) of 37.9microg Ng(-1)h(-1) and a K(m) of 104mg N-NO(3)(-)L(-1). Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4ng Ng(-1)h(-1) for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates). Copyright 2009 Elsevier Ltd. All rights reserved.
Data reduction in cascade impactor and sedimentation battery
International Nuclear Information System (INIS)
Boulaud, Denis; Diouri, Mohamed.
The determination of the mass distribution of an aerosol from data collected by a cascade impactor or a sedimentation battery implies the size characterization of each impactor stage or each battery length. In the case of the impactor four data reduction methods were compared. Preinning and Picknett's methods, a simulation method and the wellknown effective cut off size method. A theoretical simulation showed that both the simulation and Picknett's methods were the best adapted to restituting a mass distribution with an uncertainty not exceeding 5% for the mass median diameter and 10% for the standard deviation. In the case of the sedimentation battery a new method was developed allowing data reduction when the analytical shape of the size distribution is known. A theoretical simulation was carried out in order to test our method. The test showed that this method was also adapted to restituting the distribution shape, however the size range covered by the sedimentation battery was generally smaller than that of the impactor [fr
Thiosulfate and sulfite distributions in porewater of marine sediments related to manganese, iron, and sulfur geochemistry
Thamdrup, Bo; Finster, Kai; Fossing, Henrik; Hansen, Jens Würgler; Jørgensen, Bo Barker
Depth distributions of thiosulfate (S 2O 32-) and sulfite (SO 32-) were measured in the porewaters of a Danish salt marsh and subtidal marine sediments by HPLC analysis after derivatization with DTNP [2,2'-dithiobis(5-nitropyridine)]. The distributions were compared to the redox zonation as indicated by Eh and Mn 2+, Fe 2+ and H 2S distributions. Concentrations of S 2O 32- varied from below detection (<50 nM) to 600 nM while SO 32- concentrations generally were 2-3 times higher, 100-1500 nM. Depth distributions of the two species were roughly similar. Lowest concentrations were found in the oxidized zone, including both the oxic surface layer and the suboxic zone of intense manganese and iron reduction, and concentrations tended to increase through the suboxic and into the reduced, sulfidic zone. The similarity of SO 32- and S 2O 32- profiles suggested a close coupling of the cycling of the two species. Rates of consumption were suggested as the main factor governing their distribution. Rapid turnover times for S 2O 32- and H 2S of 4 and 1.1 h, respectively, were estimated for the upper 0-1 cm of a subtidal sediment.
Distinct microbial populations are tightly linked to the profile of dissolved iron in the methanic sediments of the Helgoland mud area, North Sea
Directory of Open Access Journals (Sweden)
Oluwatobi Emmanuel Oni
Full Text Available Iron reduction in subseafloor sulfate-depleted and methane-rich marine sediments is currently a subject of interest in subsurface geomicrobiology. While iron reduction and microorganisms involved have been well studied in marine surface sediments, little is known about microorganisms responsible for iron reduction in deep methanic sediments. Here, we used quantitative PCR (Q-PCR-based 16S rRNA gene copy numbers and pyrosequencing-based relative abundances of bacteria and archaea to investigate covariance between distinct microbial populations and specific geochemical profiles in the top 5 m of sediment cores from the Helgoland mud area, North Sea. We found that gene copy numbers of bacteria and archaea were specifically higher around the peak of dissolved iron in the methanic zone (250-350 cm. The higher copy numbers at these depths were also reflected by the relative sequence abundances of members of the candidate division JS1, methanogenic and Methanohalobium/ANME-3 related archaea. The distribution of these populations was strongly correlated to the profile of pore-water Fe2+ while that of Desulfobacteraceae corresponded to the pore-water sulfate profile. Furthermore, specific JS1 populations also strongly co-varied with the distribution of Methanosaetaceae in the methanic zone. Our data suggest that the interplay among JS1 bacteria, methanogenic archaea and Methanohalobium/ANME-3-related archaea may be important for iron reduction and methane cycling in deep methanic sediments of the Helgoland mud area and perhaps in other methane-rich depositional environments.
The Rusty Sink: Iron Promotes the Preservation of Organic Matter in Sediments
Lalonde, K. M.; Mucci, A.; Moritz, A.; Ouellet, A.; Gelinas, Y.
The biogeochemical cycles of iron (Fe) and organic carbon (OC) are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved Fe [1], whereas in soils, solid Fe phases provide a sheltering and preservative effect for organic matter [2]. Until now however, the role of iron in the preservation of OC in sediments has not been clearly established. Here we show that 21.5 ± 8.6% of the OC in sediments is directly bound to reactive iron phases, which promote the preservation of OC in sediments. Iron-bound OC represents a global mass of 19 to 45 × 10^15 g of OC in surface marine sediments. This pool of OC is different from the rest of sedimentary OC, with 13C and nitrogen-enriched organic matter preferentially bound to Fe which suggests that biochemical fractionation occurs with OC-Fe binding. Preferential binding also affects the recovery of high molecular weight lipid biomarkers and acidic lignin oxidation products, changing the environmental message of proxies derived from these biomarkers. [1] Johnson, K. S., Gordon, R. M. & Coale, K. H. What controls dissolved iron in the world ocean? Marine Chemistry 57, 137-161 (1997). [2] Kaiser, K. & Guggenberger, G. The role of DOM sorption to mineral surfaces in the preservation of organic matter in soils. Organic Geochemistry 31, 711-725 (2000).
Iron ore pollution in Mandovi and Zuari estuarine sediments and its fate after mining ban.
Kessarkar, Pratima M; Suja, S; Sudheesh, V; Srivastava, Shubh; Rao, V Purnachandra
Iron ore was mined from the banded iron formations of Goa, India, and transported through the Mandovi and Zuari estuaries for six decades until the ban on mining from September 2012. Here we focus on the environmental magnetic properties of sediments from the catchment area, upstream and downstream of these estuaries, and adjacent shelf during peak mining time. Magnetic susceptibility (χ lf) and saturation isothermal remanent magnetization (SIRM) values of sediments were highest in upstream (catchment area and estuaries), decreased gradually towards downstream (catchment area and estuaries), and were lowest on the adjacent shelf. The χ lf values of the Mandovi estuary were two to fourfold higher than those in the Zuari. The sediments of these two estuaries after the mining ban showed enrichment of older magnetite and sharp decrease in the SIRM values. Although the input of ore material has been reduced after mining ban, more flushing of estuarine sediments is required for healthier environment.
Moessbauer investigation of characteristic distribution of iron oxides in sediments from the Antarctica
International Nuclear Information System (INIS)
Kuzmann, E.; Homonnay, Z.; Vertes, A.; Garg, V.K.; De Oliveira, A.C.; De Souza Junior, P.A.; Schuch, L.A.
Sediments from the Admirally Bay, King George Island, Antarctica, were investigated by 57 Fe Moessbauer spectroscopy, X-ray diffractometry, and radiometry. Quartz, feldspar, chlorite, calcite, dolomite, mica, kaolinite, hematite and magnetite were identified as constituent minerals in the sediment samples. The phase composition and the iron distribution among the crystallographic sites of iron-bearing minerals (silicates, magnetite and hematite) of samples from different location have been derived from the complex Moessbauer spectra. At different locations sediments has significant characteristic differences in the mineral composition, in the iron distribution among the crystallographic site of silicates, and in the specific radioactivity of Cs radionuclides. These results indicate differences in the rock formation and alteration by the sediments in this maritime part of Antarctica. There is a much higher amount of iron oxides in the sediments from south part of the geological fault across the Admirally Bay than in the north part. This can be associated with much more alteration in the rocks in the south part compared to the northern one. This finding can contribute to the question of the history of the formation and alteration of volcanic rocks in the border of Antarctica. (author)
Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese
Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm
A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835
Experimental study and modelling of iron ore reduction by hydrogen
International Nuclear Information System (INIS)
Wagner, D.
In an effort to find new ways to drastically reduce the CO 2 emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterizations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen process. (author)
Phosphorus binding by poorly crystalline iron oxides in North Sea sediments
Slomp, C.P.; Gaast, S. J. van der; Raaphorst, W. van
Differential X-ray powder diffraction (DXRD) and extraction procedures were used to characterize the iron oxides present in four sediments from contrasting environments in the North Sea. Stations were located in depositional areas on the southern shelf (German Bight) and on the north-eastern
Speciation of iron and manganese in the sediments of Mandovi Estuary
Digital Repository Service at National Institute of Oceanography (India)
Jayakumar, D.A.; Rajendran, A.
Several attempts have been made to study the distribution of iron and manganese in Mandovi Estuary, Goa, India. But this is the first report of its kind on the speciation of these metals in sediments from Indian waters. This study would be useful...
Geochemical variability of copper and iron in Oman margin sediments
Digital Repository Service at National Institute of Oceanography (India)
Alagarsamy, R.
] below the oxygen minimum zone (OMZ) during RRS Discovery cruise 211/94 (Fig.1; Table 1). Sediment samples were immediately frozen (-20 ˚ C) on board prior to transport to the laboratory where they were freeze-dried and stored at -20 ˚ C prior... in the laboratory. 2.1. Analytical Methods Sediment grain size distribution in each section of cores collected below the OMZ was determined with a Coulter Counter (Model LS 130). Water content in each section of cores collected below the OMZ was determined...
Early diagenesis in the sediments of the Congo deep-sea fan dominated by massive terrigenous deposits: Part II - Iron-sulfur coupling
Taillefert, Martial; Beckler, Jordon S.; Cathalot, Cécile; Michalopoulos, Panagiotis; Corvaisier, Rudolph; Kiriazis, Nicole; Caprais, Jean-Claude; Pastor, Lucie; Rabouille, Christophe
Deep-sea fans are well known depot centers for organic carbon that should promote sulfate reduction. At the same time, the high rates of deposition of unconsolidated metal oxides from terrigenous origin may also promote metal-reducing microbial activity. To investigate the eventual coupling between the iron and sulfur cycles in these environments, shallow sediment cores (Congo River deep-sea fan ( 5000 m) were profiled using a combination of geochemical methods. Interestingly, metal reduction dominated suboxic carbon remineralization processes in most of these sediments, while dissolved sulfide was absent. In some 'hotspot' patches, however, sulfate reduction produced large sulfide concentrations which supported chemosynthetic-based benthic megafauna. These environments were characterized by sharp geochemical boundaries compared to the iron-rich background environment, suggesting that FeS precipitation efficiently titrated iron and sulfide from the pore waters. A companion study demonstrated that methanogenesis was active in the deep sediment layers of these patchy ecosystems, suggesting that sulfate reduction was promoted by alternative anaerobic processes. These highly reduced habitats could be fueled by discrete, excess inputs of highly labile natural organic matter from Congo River turbidites or by exhumation of buried sulfide during channel flank erosion and slumping. Sulfidic conditions may be maintained by the mineralization of decomposition products from local benthic macrofauna or bacterial symbionts or by the production of more crystalline Fe(III) oxide phases that are less thermodynamically favorable than sulfate reduction in these bioturbated sediments. Overall, the iron and sulfur biogeochemical cycling in this environment is unique and much more similar to a coastal ecosystem than a deep-sea environment.
Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake
Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.
Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.
Electrochemical depassivation of zero-valent iron for trichloroethene reduction
Energy Technology Data Exchange (ETDEWEB)
Chen, Liang [Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Jin, Song [Department of Civil and Architectural Engineering, University of Wyoming, Laramie, WY 82071 (United States); Advanced Environmental Technologies, LLC, Fort Collins, CO 80524 (United States); Fallgren, Paul H. [Department of Civil Engineering, University of Colorado Denver, Denver, CO 80217 (United States); Swoboda-Colberg, Norbert G. [Department of Geology and Geophysics, University of Wyoming, Laramie, WY 82071 (United States); Liu, Fei [Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of Geosciences, Beijing 100083 (China); Colberg, Patricia J.S., E-mail: firstname.lastname@example.com [Department of Civil and Architectural Engineering, University of Wyoming, Laramie, WY 82071 (United States)
Highlights: Black-Right-Pointing-Pointer Electrical current may depassivate ZVI and restore its capacity to reduce TCE. Black-Right-Pointing-Pointer Electrical current may defer or even prevent surface oxidation of ZVI. Black-Right-Pointing-Pointer Electrical current coupled with ZVI achieves greater TCE reduction than ZVI alone. - Abstract: Permeable reactive barriers (PRBs) composed of zero-valent iron (ZVI) are susceptible to passivation, resulting in substantially decreased rates of chlorinated solvent removal over time. In this study, the application of low electrical direct current (DC) to restore the reductive capacity of passivated ZVI was examined. Electrical current was applied to a laboratory column reactor filled with a mixture of pre-passivated ZVI and sand. Variable voltage settings (0-12 V) were applied through two stainless steel electrodes placed at the ends of the reactor. While only partial restoration of the reductive capacity of the passivated ZVI was observed, higher rates of trichloroethene (TCE) removal were always obtained when current was applied, and the rates of TCE removal were roughly proportional to the voltage level. Although differences were observed between the rates and extent of TCE removal within the column, it is noteworthy that TCE removal was not restricted to that region of the column where the electrons entered (i.e., at the cathode). While complete 'depassivation' of ZVI may be difficult to achieve in practice, the application of DC demonstrated observable restoration of reactivity of the passivated ZVI. This study provides evidence that this approach may significantly extend the life of a ZVI PRB.
Electrochemical depassivation of zero-valent iron for trichloroethene reduction
International Nuclear Information System (INIS)
Chen, Liang; Jin, Song; Fallgren, Paul H.; Swoboda-Colberg, Norbert G.; Liu, Fei; Colberg, Patricia J.S.
Highlights: ► Electrical current may depassivate ZVI and restore its capacity to reduce TCE. ► Electrical current may defer or even prevent surface oxidation of ZVI. ► Electrical current coupled with ZVI achieves greater TCE reduction than ZVI alone. - Abstract: Permeable reactive barriers (PRBs) composed of zero-valent iron (ZVI) are susceptible to passivation, resulting in substantially decreased rates of chlorinated solvent removal over time. In this study, the application of low electrical direct current (DC) to restore the reductive capacity of passivated ZVI was examined. Electrical current was applied to a laboratory column reactor filled with a mixture of pre-passivated ZVI and sand. Variable voltage settings (0–12 V) were applied through two stainless steel electrodes placed at the ends of the reactor. While only partial restoration of the reductive capacity of the passivated ZVI was observed, higher rates of trichloroethene (TCE) removal were always obtained when current was applied, and the rates of TCE removal were roughly proportional to the voltage level. Although differences were observed between the rates and extent of TCE removal within the column, it is noteworthy that TCE removal was not restricted to that region of the column where the electrons entered (i.e., at the cathode). While complete "depassivation" of ZVI may be difficult to achieve in practice, the application of DC demonstrated observable restoration of reactivity of the passivated ZVI. This study provides evidence that this approach may significantly extend the life of a ZVI PRB.
Enhanced reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide
International Nuclear Information System (INIS)
Li, F.B.; Li, X.M.; Zhou, S.G.; Zhuang, L.; Cao, F.; Huang, D.Y.; Xu, W.; Liu, T.X.; Feng, C.H.
The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (α-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of α-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe 2+ + α-FeOOH and the system of DIRB + α-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of α-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments. - This is the first case reporting the reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide.
Enhanced reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide
Energy Technology Data Exchange (ETDEWEB)
Li, F.B., E-mail: email@example.com [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Li, X.M. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Zhou, S.G.; Zhuang, L. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Cao, F. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Huang, D.Y.; Xu, W.; Liu, T.X. [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Feng, C.H. [School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641 (China)
The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (alpha-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of alpha-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe{sup 2+} + alpha-FeOOH and the system of DIRB + alpha-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of alpha-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments. - This is the first case reporting the reductive dechlorination of DDT in an anaerobic system of dissimilatory iron-reducing bacteria and iron oxide.
Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon.
Lewis, Ariel S; Huntington, Thomas G; Marvin-DiPasquale, Mark C; Amirbahman, Aria
Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment. Copyright © 2015 Elsevier Ltd. All rights reserved.
Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon
Lewis, Ariel S.; Huntington, Thomas G.; Marvin-DiPasquale, Mark C.; Amirbahman, Aria
Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.
Iron geochemistry and organic carbon preservation by iron (oxyhydr)oxides in surface sediments of the East China Sea and the south Yellow Sea
Ma, Wei-Wei; Zhu, Mao-Xu; Yang, Gui-Peng; Li, Tie
In marine sediments factors that influence iron (Fe) geochemistry and its interactions with other elements are diverse and remain poorly understood. Here we comparatively study Fe speciation and reactive Fe-bound organic carbon (Fe-OC) in surface sediments of the East China Sea (ECS) and the south Yellow Sea (SYS). The objectives are to better understand the potential impacts of geochemically distinct sediment sources and depositional/diagenetic settings on Fe geochemistry and OC preservation by Fe (hydr)oxides in sediments of the two extensive shelf seas around the world. Contents of carbonate- and acid-volatile-sulfide (AVS)-associated Fe(II) (FeAVS + carb) and magnetite (Femag) in the ECS sediments are about 5 and 9 times higher, respectively, than in the SYS. This could be ascribed to the ferruginous conditions of the ECS sediments that favor the formation/accumulation of Fecarb and Femag, a unique feature of marine unsteady depositional regimes. Much lower total Fe(II) contents in the SYS than in the ECS suggest that lower availability of highly reactive Fe (FeHR) and/or weak Fe reduction is a factor limiting Fe(II) formation and accumulation in the SYS sediments. The ratio of FeHR to total Fe is, on average, markedly higher (2.4 times) in the ECS sediments than in the SYS, which may be a combined result of several factors relevant to different sediment sources and depositional/diagenetic settings. In comparison with many other marine sediments, the percent fractions (fFe-OC) of Fe-OC to total organic carbon (TOC) in the ECS and the SYS are low, which can be ascribed to surface adsorption of OC rather than coprecipitation or organic complexation as the dominant binding mechanisms. Based on the fFe-OC in this study, total Fe-OC estimated for global continental shelves is equivalent to 38% of the atmospheric CO2 pool, which indicates the important role of sorptive stabilization of Fe-OC in continental shelf sediments for buffering CO2 release to the atmosphere
Microbial Reduction of Fe(III) in Acidic Sediments: Isolation of Acidiphilium cryptum JF-5 Capable of Coupling the Reduction of Fe(III) to the Oxidation of Glucose
Küsel, Kirsten; Dorsch, Tanja; Acker, Georg; Stackebrandt, Erko
To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12°C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H2 was consumed by acid...
Control of manganese and iron in Skagerrak sediments (northeastern North Sea)
Digital Repository Service at National Institute of Oceanography (India)
Rajendran, A.; DileepKumar, M.; Bakker, J.F.
- 80. I00 E E 40" "I- l-- n 6Or hl 80" ioo (a) MANGANESE ( mmo\\[. kg ''1 ) ,? 2,0 3p ~, A ,o =o 40" 6O" I00 B (b) IRON (mmol. kg '-I ) 4o 6o- 8O" IO( ~o,oo ,ooo i I I 590 I A o 20- . 40" 60" ,J o 2o 40" 60" 80- IOO... in these sediments, expressed as change in concentration with time on a volume basis of sediments or pore water \\[see Berner (1980) for a discussion \\], the steady-state equations of Burdige and Gieskes (1983) have been used. These are, ( 1 ) oxic zone...
Iron ore pollution in Mandovi and Zuari estuarine sediments and its fate after mining ban
Digital Repository Service at National Institute of Oceanography (India)
Kessarkar, P.M.; Suja, S.; Sudheesh, V.; Srivastava, S.; Rao, V.P.
). Another possibility could be formation of ferritized iron crust (Mathe et al. 1997) during lateritic weathering. Magnetic properties of upstream sediments of Ma-Zu estuaries Sediments from the upstream of Mandovi (M6-M9) and Zuari (Z6-Z9) estuaries... for late Quaternary climatic change. Marine Geology, 220, 59-82. Maher, B. A., & Taylor, R. M. (1988). Formation of ultrafine-grained magnetite in soils. Nature, 336, 368-370. Mathe, P. E., Rochette, P., & Colin, F. (1997). The origin of magnetic...
Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks
Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.
The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex
Rodriguez, Meghan M.; Bill, Eckhard; Brennessel, William W.; Holland, Patrick L.
The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N2) to ammonia is an iron surface promoted with K+, but soluble iron complexes have neither reduced the N-N bond of N2 to nitride nor produced large amounts of NH3 from N2. We report a molecular iron complex that reacts with N2 and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe3N2 core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H2 to give substantial yields of N2-derived ammonia. These reactions, though not yet catalytic, give structural and spectroscopic insight into N2 cleavage and N-H bond-forming reactions of iron. PMID:22076372
N₂reduction and hydrogenation to ammonia by a molecular iron-potassium complex.
Rodriguez, Meghan M; Bill, Eckhard; Brennessel, William W; Holland, Patrick L
The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron.
Microbial dissimilatory iron(III) reduction: Studies on the mechanism and on processes of environmental relevance
Jahn, Michael
Many microbes are able to respire aerobically oxygen or anaerobically other electron acceptors for example sulphate, nitrate, manganese(IV) or Fe(III). As iron minerals are widespread in nature, dissimilatory iron(III) reduction by different microorganisms is a very important process of anaerobic respiration. The general goal of this work was to improve the knowledge of processes, in which iron-reducing microbes are said to play an important role. For this purpose, in one part the focus wa...
Riboflavin Biosynthesis Is Associated with Assimilatory Ferric Reduction and Iron Acquisition by Campylobacter Jejuni.
Gaskin, D.J.H.; Holmes, K.; Mulholland, F.; Wells, J.
One of the pathways involved in the acquisition of the essential metal iron by bacteria involves the reduction of insoluble Fe3+ to soluble Fe2+, followed by transport of Fe2+ to the cytoplasm. Flavins have been implicated as electron donors in this poorly understood process. Ferrous iron uptake is
Seasonal variation of iron speciation in a pearl-raising bay sediment by Moessbauer spectroscopy
International Nuclear Information System (INIS)
Kuno, Akihito; Matsuo, Motoyuki; Chiba, Satoshi; Yamagata, Yoichi
Ago Bay in Mie Prefecture, central Japan, is world-famous for the site of Mikimoto pearl culture, but recently the production of pearls has considerably declined. Environmental deterioration of the bay is suspected of having caused the decline. The periodic investigation into iron speciation of the bay sediment by 57 Fe Moessbauer spectroscopy revealed its high pyrite (FeS 2 ) content from the surface to the 20-cm depth. The pyrite in the surface sediment decreased only in spring, three months after the dissolved oxygen in the bottom water was at maximum. Such oxygen-consuming material as pyrite accumulated through long-term biotic activity is a most-likely explanation for the prolonged environmental deterioration of the bay, which appears in the high chemical oxygen demand (COD) of the sediment. (author)
Reactivity of Organic Matter and other Reductants in Aquifer Sediments
Hartog, N.
The molecular composition and the carbon isotope signature of sedimentary organic matter (SOM) and indicate that SOM is predominantly derived from higher land plants in sediments of both terrestrial as marine origins. The reactivity of SOM in the aquifer sediments studied is determined by the extent
Natural clinoptilolite exchanged with iron: characterization and catalytic activity in nitrogen monoxide reduction
Directory of Open Access Journals (Sweden)
Daria Tito-Ferro
Full Text Available The aim of this work was to characterize the natural clinoptilolite from Tasajeras deposit, Cuba, modified by hydrothermal ion-exchange with solutions of iron (II sulfate and iron (III nitrate in acid medium. Besides this, its catalytic activity to reduce nitrogen monoxide with carbon monoxide/propene in the presence of oxygen was evaluated. The characterization was performed by Mössbauer and UV-Vis diffuse reflectance spectroscopies and adsorption measurements. The obtained results lead to conclude that in exchanged samples, incorporated divalent and trivalent irons are found in octahedral coordination. Both irons should be mainly in cationic extra-framework positions inside clinoptilolite channels as charge compensating cations, and also as iron oxy-hydroxides resulting from limited hydrolysis of these cations. The iron (III exchanged samples has a larger amount of iron oxy-hydroxides agglomerates. The iron (II exchanged samples have additionally iron (II sulfate adsorbed. The catalytic activity in the nitrogen monoxide reduction is higher in the exchanged zeolites than starting. Among all samples, those exchanged of iron (II has the higher catalytic activity. This lead to outline that, main catalytically active centers are associated with divalent iron.
Assessing Sediment Yield and the Effect of Best Management Practices on Sediment Yield Reduction for Tutuila Island, American Samoa
Leta, O. T.; Dulai, H.; El-Kadi, A. I.
Upland soil erosion and sedimentation are the main threats for riparian and coastal reef ecosystems in Pacific islands. Here, due to small size of the watersheds and steep slope, the residence time of rainfall runoff and its suspended load is short. Fagaalu bay, located on the island of Tutuila (American Samoa) has been identified as a priority watershed, due to degraded coral reef condition and reduction of stream water quality from heavy anthropogenic activity yielding high nutrients and sediment loads to the receiving water bodies. This study aimed to estimate the sediment yield to the Fagaalu stream and assess the impact of Best Management Practices (BMP) on sediment yield reduction. For this, the Soil and Water Assessment Tool (SWAT) model was applied, calibrated, and validated for both daily streamflow and sediment load simulation. The model also estimated the sediment yield contributions from existing land use types of Fagaalu and identified soil erosion prone areas for introducing BMP scenarios in the watershed. Then, three BMP scenarios, such as stone bund, retention pond, and filter strip were treated on bare (quarry area), agricultural, and shrub land use types. It was found that the bare land with quarry activity yielded the highest annual average sediment yield of 133 ton per hectare (t ha-1) followed by agriculture (26.1 t ha-1) while the lowest sediment yield of 0.2 t ha-1 was estimated for the forested part of the watershed. Additionally, the bare land area (2 ha) contributed approximately 65% (207 ha) of the watershed's sediment yield, which is 4.0 t ha-1. The latter signifies the high impact as well as contribution of anthropogenic activity on sediment yield. The use of different BMP scenarios generally reduced the sediment yield to the coastal reef of Fagaalu watershed. However, treating the quarry activity area with stone bund showed the highest sediment yield reduction as compared to the other two BMP scenarios. This study provides an estimate
Influence of sulfate reduction on the organic matter of Wealden sediments of the Lower Saxony Basin (Germany)
Energy Technology Data Exchange (ETDEWEB)
Berner, U. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany)
Sediments of the Wealden (Lower Saxony Basin, Germany) as obtained from the well Isterberg 1001 consist of clay stones, marls and few massive carbonate horizons. Although, the basin is predominantly characterized as lacustrine geochemical data indicate significant influences of marine ingression which have introduced sulfur into the depositional system. Consequently the organic matter of the sediments has been substantially affected by bacterial sulfate reduction, which has led to losses of the initial organic carbon of 5 to 80 wt.- percent, which is a minimum estimate as losses of H{sub 2}S form the sediments were not taken into account for the mass balance consideration. Complete uptake of reactive iron into sulfides has led in a significant number of samples to the presence of excess sulfur not contained in sulfides. In our argumentation we assume that excess sulfur is at least partly incorporated into the organic matter. Pyrolysis investigations show that organic matter in samples containing higher amounts of excess sulfur generates hydrocarbons at lower temperatures than samples with low concentrations of excess sulfur. These observations are compatible with findings usually reported for Type S-II kerogens. The likely organically bound excess sulfur introduces a bias with thermal maturities from RockEval pyrolysis, which implies that T{sub max} data rather reflect quality changes of the organic matter than thermal maturity in the investigated Wealden sediments. The hydrocarbon potential has been reduced significantly in samples which have been affected strongly by the microbial process as indicated by hydrogen indices of the sediments. The observations of variable degrees of sulfate reduction indicate also a variation of organic matter fluxes to the sediment surface of the palaeo-lake likely resulting from changes in biological surface productivity. Low carbon fluxes likely coincide with extensive use of organic substrate by sulfate reducers whereas high
The scavenging of silver by manganese and iron oxides in stream sediments collected from two drainage areas of Colorado
Chao, T.T.; Anderson, B.J.
Stream sediments of two well-weathered and aerated drainage areas of Colorado containing anomalous amounts of silver were allowed to react by shaking with nitric acid of different concentrations (1-10M). Silver, manganese, and iron simultaneously dissolved were determined by atomic absorption. The relationship between silver dissolution and the dissolution of manganese and/or iron was evaluated by linear and multiple regression analyses. The highly significant correlation coefficient (r = 0.913) between silver and manganese dissolution suggests that manganese oxides are the major control on the scavenging of silver in these stream sediments, whereas iron oxides only play a secondary role in this regard. ?? 1974.
Reduction of vibrational interference from the iron core on HBTXIA
International Nuclear Information System (INIS)
Wilcock, P.D.
The HBTXIA machine is a toroidal reversed field pinch which utilises a 1 volt second iron core. This paper looks briefly at the sources of vibration from the iron core and describes the design of a novel support system that has been installed to minimise the transmission of vibration to plasma diagnostics and other equipment during the machine pulse. Vibration measurements on the completed installation when the core is driven to saturation are reported and compared with calculations for a ground mounted core. (author)
Utilization potentiality of coal as a reductant for the production of sponge iron. [5 refs
Energy Technology Data Exchange (ETDEWEB)
Mishra, H P
With the ambitious plan of the Government of India to produce about 70 million tonnes of steel per annum towards the end of the century, the requirement of coal would be enormous. This calls for judicious planning and conservation of coal. Modern trend in steel plant practice is to use blast furnaces of capacity 10,000 to 12,000 t/day requiring superior quality coke of low ash content which will become scarce. Concerted efforts should be made to by-pass blast furnace technique by adopting direct reduction for the production of metallized iron ore, that is sponge iron, and using this as feed stock in electric furnaces. Experience has shown that the use of sponge iron as feed stock for electric arc furnaces instead of the scrap available from various fabrication and steel works results in better production of alloy steels. The use of non-coking coal as reductant for production of sponge iron will help conserve coking coal for bigger steel plants. In the solid state reduction process the technological design of the sponge iron plant has to be tailored to the type of feed stock to be used, particularly iron ore and coal. In India, non-coking coal is available at close proximity to the iron ore mines containing high grade iron ore. Planning for sponge iron, utilizing large reserves of non-coking coal as feed stock therefore has considerable potentiality. India has vast reserves of high grade iron ore and comparatively meager amount of coking coal. This calls for planning for sponge iron using non-coking coal as feed stock.
Bacterial disproportionation of elemental sulfur coupled to chemical reduction of iron or manganese
DEFF Research Database (Denmark)
Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler
and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S was microbially disproportionated to sulfate and sulfide, as follows: 4S + 4H(2)O --> SO(4) + 3H(2)S + 2H. Subsequent chemical reactions between...... reduction of MnO(2) to Mn. Growth of small rod-shaped bacteria was observed. When incubated without MnO(2), the culture did not grow but produced small amounts of SO(4) and H(2)S at a ratio of 1:3, indicating again a disproportionation of S. The observed microbial disproportionation of S only proceeds...... significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S disproportionation in the presence of FeOOH or MnO(2) was high, > 10 cm in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic...
Biostimulation of Iron Reduction and Uranium Immobilization: Microbial and Mineralogical Controls
International Nuclear Information System (INIS)
Joel E. Kostka
This project represented a joint effort between Florida State University (FSU), Rutgers University (RU), and the University of Illinois (U of I). FSU served as the lead institution and Dr. J.E. Kostka was responsible for project coordination, integration, and deliverables. This project was designed to elucidate the microbial ecology and geochemistry of metal reduction in subsurface environments at the U.S. DOE-NABIR Field Research Center at Oak Ridge, Tennessee (ORFRC). Our objectives were to: (1) characterize the dominant iron minerals and related geochemical parameters likely to limit U(VI) speciation, (2) directly quantify reaction rates and pathways of microbial respiration (terminal-electron-accepting) processes which control subsurface sediment chemistry, and (3) identify and enumerate the organisms mediating U(VI) transformation. A total of 31 publications and 47 seminars or meeting presentations were completed under this project. One M.S. thesis (by Nadia North) and a Ph.D. dissertation (by Lainie Petrie-Edwards) were completed at FSU during fall of 2003 and spring of 2005, respectively. Ph.D. students, Denise Akob and Thomas Gihring have continued the student involvement in this research since fall of 2004. All of the above FSU graduate students were heavily involved in the research, as evidenced by their regular attendance at PI meetings and ORFRC workshops
Reduction of iron-bearing lunar minerals for the production of oxygen
Massieon, Charles; Cutler, Andrew; Shadman, Farhang
The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.
Pathways and Microbiology of Thiosulfate Transformations and Sulfate Reduction in a Marine Sediment (Kattegat, Denmark)
DEFF Research Database (Denmark)
Reductive and oxidative pathways of the sulfur cycle were studied in a marine sediment by parallel radiotracer experiments with (SO4(2-))-S-35, (H2S)-S-35, and (S2O3(2-))-S-35 injected into undisturbed sediment cores. The distributions of viable populations of sulfate- and thiosulfate-reducing ba...
Bacterial sulfate reduction in hydrothermal sediments of the Guaymas Basin, Gulf of California, Mexico
DEFF Research Database (Denmark)
Weber, A.; Jørgensen, BB
Depth distribution and temperature dependence of bacterial sulfate reduction were studied in hydrothermal surface sediments of the southern trough of the Guaymas Basin at 2000 m water depth. In situ temperatures ranged from 2.8 degreesC at the sediment surface to > 130degreesC at 30 cm depth in t...
Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile
Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker
The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the
Mechanism of the reduction of hexavalent chromium by organo-montmorillonite supported iron nanoparticles
Energy Technology Data Exchange (ETDEWEB)
Wu, Pingxiao, E-mail: email@example.com [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Li, Shuzhen [School of Chemical and Environmental Engineering, Wuyi University, Jiangmen, Guangdong Province 529020 (China); Ju, Liting [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Zhu, Nengwu [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); The Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Regular Higher Education Institutions (China); Wu, Jinhua; Li, Ping [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); Dang, Zhi [College of Environmental Science and Engineering, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); The Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Regular Higher Education Institutions (China)
Highlights: Black-Right-Pointing-Pointer Organo-montmorillonite supported iron nanoparticles were found to be more efficient in the removal of Cr(VI) than unsupported iron nanoparticles. Black-Right-Pointing-Pointer The iron nanoparticles were accommodated by the sectional structure of the clay minerals which were helpful to protect the nanoparticles from aggregating. Black-Right-Pointing-Pointer XPS and XANES provided some direct information about the reduction mechanisms. Black-Right-Pointing-Pointer The structure of the supported iron nanoparticles was stable in the reaction with Cr(VI). - Abstract: Iron nanoparticles exhibit greater reactivity than micro-sized Fe{sup 0}, and they impart advantages for groundwater remediation. In this paper, supported iron nanoparticles were synthesized to further enhance the speed and efficiency of remediation. Natural montmorillonite and organo-montmorillonite were chosen as supporting materials. The capacity of supported iron nanoparticles was evaluated, compared to unsupported iron nanoparticles, for the reduction of aqueous Cr(VI). The reduction of Cr(VI) was much greater with organo-montmorillonite supported iron nanoparticles and fitted the pseudo-second order equation better. With a dose at 0.47 g/L, a total removal capacity of 106 mg Cr/g Fe{sup 0} was obtained. Other factors that affect the efficiency of Cr(VI) removal, such as pH values, the initial Cr(VI) concentration and storage time of nanoparticles were investigated. X-ray photoelectron spectrometry (XPS) and X-ray absorption near edge structure (XANES) were used to figure out the mechanism of the removal of Cr(VI). XPS indicated that the Cr(VI) bound to the particle surface was completely reduced to Cr(III) under a range of conditions. XANES confirmed that the Cr(VI) reacted with iron nanoparticles was completely reduced to Cr(III).
Mechanism of the reduction of hexavalent chromium by organo-montmorillonite supported iron nanoparticles
International Nuclear Information System (INIS)
Wu, Pingxiao; Li, Shuzhen; Ju, Liting; Zhu, Nengwu; Wu, Jinhua; Li, Ping; Dang, Zhi
Highlights: ► Organo-montmorillonite supported iron nanoparticles were found to be more efficient in the removal of Cr(VI) than unsupported iron nanoparticles. ► The iron nanoparticles were accommodated by the sectional structure of the clay minerals which were helpful to protect the nanoparticles from aggregating. ► XPS and XANES provided some direct information about the reduction mechanisms. ► The structure of the supported iron nanoparticles was stable in the reaction with Cr(VI). - Abstract: Iron nanoparticles exhibit greater reactivity than micro-sized Fe 0 , and they impart advantages for groundwater remediation. In this paper, supported iron nanoparticles were synthesized to further enhance the speed and efficiency of remediation. Natural montmorillonite and organo-montmorillonite were chosen as supporting materials. The capacity of supported iron nanoparticles was evaluated, compared to unsupported iron nanoparticles, for the reduction of aqueous Cr(VI). The reduction of Cr(VI) was much greater with organo-montmorillonite supported iron nanoparticles and fitted the pseudo-second order equation better. With a dose at 0.47 g/L, a total removal capacity of 106 mg Cr/g Fe 0 was obtained. Other factors that affect the efficiency of Cr(VI) removal, such as pH values, the initial Cr(VI) concentration and storage time of nanoparticles were investigated. X-ray photoelectron spectrometry (XPS) and X-ray absorption near edge structure (XANES) were used to figure out the mechanism of the removal of Cr(VI). XPS indicated that the Cr(VI) bound to the particle surface was completely reduced to Cr(III) under a range of conditions. XANES confirmed that the Cr(VI) reacted with iron nanoparticles was completely reduced to Cr(III).
Redox transformation and reductive immobilization of Cr(VI) in the Columbia River hyporheic zone sediments
Energy Technology Data Exchange (ETDEWEB)
Xu, Fen; Liu, Yuanyuan; Zachara, John M.; Bowden, Mark E.; Kennedy, David W.; Plymale, Andrew E.; Liu, Chongxuan,
An experimental and modeling study was conducted to investigate the redox transformation and reductive immobilization of groundwater contaminant Cr in hyporheic zone (HZ) sediments from U.S. Department of Energy's Hanford site, where groundwater Cr(VI) is migrating and discharging to the nearby Columbia River. Experimental results revealed that Cr(VI) can be reduced to immobile reduced Cr by the HZ sediments in the presence/absence of O2. Anaerobic pre-incubation of the sediments increased the effective rate of Cr reduction that was correlated with the increase in HCl-extractable Fe(II) content in the sediments. The reduced Cr was stable in exposure to O2 under field-relevant pH (~7.5) and Mn-containing (~0.02% w/w) conditions. The Cr(VI) reduction rate showed a multi-rate behavior, apparently reflecting the presence of reductants with different reactivity in the sediments. The results from this study indicated that the HZ sediments can reductively immobilize Cr and the sediment redox capacity can be recharged through microbial activities. The results implied that HZ can play a role as a natural permeable redox barrier for removing groundwater Cr before it discharges into a river system.
Redox transformation and reductive immobilization of Cr(VI) in the Columbia River hyporheic zone sediments
Xu, Fen; Liu, Yuanyuan; Zachara, John; Bowden, Mark; Kennedy, David; Plymale, Andrew E.; Liu, Chongxuan
An experimental and modeling study was conducted to investigate the redox transformation and reductive immobilization of groundwater contaminant Cr in hyporheic zone (HZ) sediments from U.S. DOE's Hanford Site, where groundwater Cr(VI) is migrating and discharging to the nearby Columbia River. Experimental results revealed that Cr(VI) can be reduced and immobilized by the HZ sediments in the presence/absence of O2. Anaerobic pre-incubation of the sediments increased the effective rate of Cr reduction that was correlated with the increase in HCl-extractable Fe(II) content in the sediments. The reduced Cr was stable when exposed to O2 under field-relevant pH (7.5) with and without dissolved Mn(II), which might be oxidized to form Mn(III/IV) oxides that may oxidize reduced Cr. The Cr(VI) reduction rate showed a multi-rate behavior, apparently reflecting the presence of reductants with different reactivity in the sediments. The results from this study indicated that the HZ sediments can reductively immobilize Cr and the sediment redox capacity can be recharged through microbial activities. The results implied that HZ can play a role as a natural permeable redox barrier for removing groundwater Cr before it discharges into a river system.
Directory of Open Access Journals (Sweden)
Hongqin Xue
Full Text Available In Florida, soils are mainly composed of Myakka, an acid soil characterized by a subsurface accumulation of humus and Al(III and Fe(III oxides. Downgradient of the landfills in Northwest Florida, elevated levels of iron and arsenic observations had been made in the groundwater from monitoring wells, which was attributed to the geomicrobial iron and arsenic reduction. There is thus an immediate research need for a better understanding of the reduction reactions that are responsible for the mobilization of iron and arsenic in the subsurface soil nearby landfills. Owing to the high Fe(III oxide content, As(V adsorption reactions with Fe(III oxide surfaces are particularly important, which may control As(V reduction. This research focused on the investigation of the biogeochemical processes of the subsurface soil nearby landfills of Northwest Florida. Arsenic and iron reduction was studied in batch reactors and quantified based on Monod-type microbial kinetic growth simulations. As(V adsorption in iron-rich Northwest Floridian soils was further investigated to explain the reduction observations. It was demonstrated in this research that solubilization of arsenic in the subsurface soil nearby landfills in Northwest Florida would likely occur under conditions favoring Fe(III dissimilatory reduction.
Reduction Behaviors of Carbon Composite Iron Oxide Briquette Under Oxidation Atmosphere
Energy Technology Data Exchange (ETDEWEB)
Lee, Ki-Woo; Kim, Kang-Min; Kwon, Jae-Hong; Han, Jeong-Whan [Inha University, Incheon (Korea, Republic of); Son, Sang-Han [POSCO, Pohang (Korea, Republic of)
The carbon composite iron oxide briquette (CCB) is considered a potential solution to the upcoming use of low grade iron resources in the ironmaking process. CCB is able to reduce raw material cost by enabling the use of low grade powdered iron ores and coal. Additionally, the fast reduction of iron oxides by direct contact with coal can be utilized. In this study, the reduction behaviors of CCB were investigated in the temperature range of 200-1200 ℃ under oxidizing atmosphere. Briquettes were prepared by mixing iron ore and coal in a weight ratio of 8:2. Then reduction experiments were carried out in a mixed gas atmosphere of N{sub 2}, O{sub 2}, and CO{sub 2}. Compressive strength tests and quantitative analysis were performed by taking samples at each target temperature. In addition, the reduction degree depending on the reaction time was evaluated by off-gas analysis during the reduction test. It was found that the compressive strength and the metallization degree of the reduced briquettes increased with increases in the reaction temperature and holding time. However, it tended to decrease when the re-oxidation phenomenon was caused by injected oxygen. The degree of reduction reached a maximum value in 26 minutes. Therefore, the re-oxidation phenomenon becomes dominant after 26 minutes.
In Situ Spectroscopic Analysis of the Carbothermal Reduction Process of Iron Oxides during Microwave Irradiation
Directory of Open Access Journals (Sweden)
Jun Fukushima
Full Text Available The effects of microwave plasma induction and reduction on the promotion of the carbothermal reduction of iron oxides (α-Fe2O3, γ-Fe2O3, and Fe3O4 are investigated using in situ emission spectroscopy measurements during 2.45 GHz microwave processing, and the plasma discharge (such as CN and N2 is measured during microwave E-field irradiation. It is shown that CN gas or excited CN molecules contribute to the iron oxide reduction reactions, as well as to the thermal reduction. On the other hand, no plasma is generated during microwave H-field irradiation, resulting in thermal reduction. Magnetite strongly interacts with the microwave H-field, and the reduction reaction is clearly promoted by microwave H-field irradiation, as well as thermal reduction reaction.
Formation of ferric iron crusts in Quaternary sediments of Lake Baikal, Russia, and implications for paleoclimate
Deike, R.G.; Granina, L.; Callender, E.; McGee, J.J.
Phosphate-bearing, ferric iron and siliceous crusts ranging in age from Recent to approximately 65,000 yr B.P. are observed in sediments of Lake Baikal. In younger sediments the crusts are at the base of a spectrum of secondary iron and manganese oxides that accumulate near the sediment/water interface in the zone of positive oxidation potential beneath an oxygenated water column. In areas where the average Quaternary sedimentation rates have been slow (e.g. 0.026 mm/yr), the crusts are more common, and span a wider range of ages. No crusts have been found where the Quaternary sedimentation mode has been deltaic and rapid (0.15 mm/yr). Independent core correlation based on magnetic properties of the sediment suggests that crusts can be correlated over most of Academician Ridge, an area that is particularly sensitive to climatic events affecting the concentration of suspended sediment. These crusts may be indicative of periods of low suspended sediment concentration, which occur during sustained transitions from glacial periods of high detrital input, to interglacial periods of high diatom sedimentation. The crusts are dominated by iron-rich and siliceous amorphous mineral phases, with an FeO:SiO2 by weight of 3:1. Regardless of age or location in the lake the Fe phase always includes Ca, P and Mn. Extensive microprobe data for these four elements recast as normalized elemental weight percent reveal linear trends of Ca:P and Fe:P. With increasing P, Ca also increases such that the two elements maintain a linear relationship passing very close to the origin and with a mean molar Ca:P=0.3 (too low for well-characterized apatite). Conversely, with increasing P, Fe decreases (mean molar Fe:P=3.4). There is no correlation between Mn and P. Molar Fe:P ratios for vivianite (an Fe(II) phosphate mineral observed in sediments closely below some crusts) are clustered around a stoichiometric composition. The covariant increase in Ca:P and the corresponding decrease in Fe:P may
Energy Saving Melting and Revert Reduction Technology: Aging of Graphitic Cast Irons and Machinability
Energy Technology Data Exchange (ETDEWEB)
Richards, Von L. [Advanced Technology Inst., Virginia Beach, VA (United States)
The objective of this task was to determine whether ductile iron and compacted graphite iron exhibit age strengthening to a statistically significant extent. Further, this effort identified the mechanism by which gray iron age strengthens and the mechanism by which age-strengthening improves the machinability of gray cast iron. These results were then used to determine whether age strengthening improves the machinability of ductile iron and compacted graphite iron alloys in order to develop a predictive model of alloy factor effects on age strengthening. The results of this work will lead to reduced section sizes, and corresponding weight and energy savings. Improved machinability will reduce scrap and enhance casting marketability. Technical Conclusions: Age strengthening was demonstrated to occur in gray iron ductile iron and compacted graphite iron. Machinability was demonstrated to be improved by age strengthening when free ferrite was present in the microstructure, but not in a fully pearlitic microstructure. Age strengthening only occurs when there is residual nitrogen in solid solution in the Ferrite, whether the ferrite is free ferrite or the ferrite lamellae within pearlite. Age strengthening can be accelerated by Mn at about 0.5% in excess of the Mn/S balance Estimated energy savings over ten years is 13.05 trillion BTU, based primarily on yield improvement and size reduction of castings for equivalent service. Also it is estimated that the heavy truck end use of lighter castings for equivalent service requirement will result in a diesel fuel energy savings of 131 trillion BTU over ten years.
Inorganic arsenic and iron(II) distributions in sediment porewaters investigated by a combined DGTcolourimetric DET technique
DEFF Research Database (Denmark)
Bennett, William W.; Teasdale, Peter R.; Welsh, David T.
A new approach for investigating the biogeochemistry of inorganic arsenic and iron(II) in freshwater, estuarine and marine sediments is reported. The recently developed Metsorb diffusive gradients in thin films (DGT) technique for the measurement of total inorganic arsenic and the colourimetric d...... highly representative assessment of the biogeochemical status of arsenic and iron in a variety of natural sediments, including groundwater sediments where mobilised arsenic is responsible for significant human health risks.......A new approach for investigating the biogeochemistry of inorganic arsenic and iron(II) in freshwater, estuarine and marine sediments is reported. The recently developed Metsorb diffusive gradients in thin films (DGT) technique for the measurement of total inorganic arsenic and the colourimetric...... diffusive equilibration in thin films (DET) technique for the measurement of iron(II), were utilised in combination to determine co-located depth profiles of both solutes in sediment porewaters. DGT-measured porewater arsenic concentrations were typically less than 40nM, whereas iron(II) concentrations...
Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides
International Nuclear Information System (INIS)
Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.
The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves
Hydrogeochemical assessment of mine-impacted water and sediment of iron ore mining
Nur Atirah Affandi, Fatin; Kusin, Faradiella Mohd; Aqilah Sulong, Nur; Madzin, Zafira
This study was carried out to evaluate the hydrogeochemical behaviour of mine-impacted water and sediment of a former iron ore mining area. Sampling of mine water and sediment were carried out at selected locations within the mine including the former mining ponds, mine tailings and the nearby stream. The water samples were analysed for their hydrochemical facies, major and trace elements including heavy metals. The water in the mining ponds and the mine tailings was characterised as highly acidic (pH 2.54-3.07), but has near-neutral pH in the nearby stream. Results indicated that Fe and Mn in water have exceeded the recommended guidelines values and was also supported by the results of geochemical modelling. The results also indicated that sediments in the mining area were contaminated with Cd and As as shown by the potential ecological risk index values. The total risk index of heavy metals in the sediment were ranked in the order of Cd>As>Pb>Cu>Zn>Cr. Overall, the extent of potential ecological risks of the mining area were categorised as having low to moderate ecological risk.
Comparison of the Efficiencies of Zero-Valent Iron Nanoparticles and Stabilized Iron Nanoparticles for Nitrate Reduction from Polluted Waters
Directory of Open Access Journals (Sweden)
Fatemeh Nooralivand
Full Text Available The present study was conducted to evaluate the feasibility of zero-valent iron nanoparticles (ZVIN for the removal of nitrate from aqueous solutions. For this purpose, bare zero-valent iron nanoparticles (bare-ZVIN and CMC-ZVIN were synthesized using the borohydride reduction method and their morphological characteristics were examined via scanning electron microscopy (SEM, X-ray diffraction (XRD, and Fourier Transmission Infrared Spectroscopy (FTIR. The effects of pH of the aqueous solution, initial nitrate concentration, ZVIN concentration, and contact time on nitrate reduction were investigated as operational parameters and the kinetics of nitrate reduction was studied in batch experiments. The results showed that 93.65% of nitrate was removed by stabilized nanoparticles at pH=6 while non-stabilized nanoparticles at pH=2 were able to remove 85.55% of the nitrate.Furthermore, nitrate reduction was enhanced by increasing ZVIN concentration and contact time while it was decreased as a result of increasing initial nitrate concentration. The major product of nitrate reduction at an acidic pH was found to be ammonium; at an alkaline pH, however, nitrate was converted to nitrogen and nitrite production dropped to less than 2%. Kinetic analysis demonstrated that denitrification of nitrate by the nanoparticles fitted well with first-order and second-order reaction models. The results also demonstrated that the stabilized ZVI nanoparticles were more effective than bare-ZVIN for nitrate reduction in aqueous solutions.
Reduction in density of suspended - sediment - laden natural waters
Digital Repository Service at National Institute of Oceanography (India)
Joseph, A.; Desa, E.; Desa, E.; Smith, D.; Peshwe, V.B.; VijayKumar, K.; Desa, J.A.E.
to 0.4% - 4.5%) that of the density of the same water without suspended sediment. Teh values of peff in a given site differed from one tidal cycle to another (approx equal to 1.9%). These values varied slightly (less than 0.8%) from mid-tide to slack...
Microbial reductive transformation of phyllosilicate Fe(III) and U(VI) in fluvial subsurface sediments.
Lee, Ji-Hoon; Fredrickson, James K; Kukkadapu, Ravi K; Boyanov, Maxim I; Kemner, Kenneth M; Lin, Xueju; Kennedy, David W; Bjornstad, Bruce N; Konopka, Allan E; Moore, Dean A; Resch, Charles T; Phillips, Jerry L
The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.
Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes
Energy Technology Data Exchange (ETDEWEB)
Huang, Li-Zhi, E-mail: firstname.lastname@example.com [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Hansen, Hans Christian B. [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Bjerrum, Morten Jannik [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK–2100 København Ø (Denmark)
Highlights: • Composite layers of single sheet iron oxides were coated on indium tin oxide electrodes. • Single sheet iron oxide is an electro-catalyst for reduction of nitroaromatic compounds in aqueous solution. • The reduction is well explained by a diffusion layer model. • The charge properties of the nitrophenols have an important influence on reduction. • Low-cost iron oxide based materials are promising electro-catalyst for water treatment. - Abstract: Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30 μA cm{sup −2} was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400 μM of the nitroaromatic compound at a potential of −0.7 V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant = 0.28 h{sup −1}) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant = 6.9 μM h{sup −1}). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and
Assessing the potential of spectral induced polarization to detect in situ changes in iron reduction
Rosier, C. L.; Price, A.; Sharma, S.; Atekwana, E. A.
The near surface geophysical technique Spectral Induced Polarization (SIP), provides promise as an effective method measuring in situ biofilm formation/development. Yet, potential mechanisms responsible for observed shifts in SIP response due to biofilm are not clearly understood. In order to address possible mechanisms we assessed the influence of Shewanella oneidensis (MR1) cell density (colony forming units; CFU), biofilm production (Bradford assay) and iron reduction metabolism (colorimetric assay) on SIP response. Laboratory measurements were collected over three months on columns packed with either iron-coated or iron-free sands and amended with artificial ground water and acetate in order to stimulate biofilm production and microbial iron reduction. Additionally, scanning electron microscopy (SEM) was used to confirm the presence of S. oneidensis cells and biofilm. Our results suggest that during early/initial stage (75 days) of column incubation, SIP measurements revealed that phase and imaginary conductivity responses decreased as the concentration of reduced iron decreased below 2.0 mM. In contrast, we observed only a moderate increase in phase and imaginary conductivity ( 30%) within iron-free columns as a result of increases in S. oneidensis cells (CFU 1.5 x 1011) and biofilm production (7.0 mg ml-1). SEM analysis confirmed the presence of biofilm and cells within both iron-coated and iron-free columns. We hypothesize that the production of microbial metabolic byproducts is a potential mechanism explaining large phase shits observed in previous studies ( 50 mrads) rather than the conductivity of cells or biofilm. Our findings provide support for the following: i) ratio of cells to biofilm production only moderately influences both phase and imaginary conductivity response and ii) largest phase and imaginary conductivity response resulted from microbial metabolism (i.e. iron reduction) and potentially biofilm trapping of conductive materials (i
Assessment of the Efficiency of Sediment Deposition Reduction in the Zengwen River Watershed in Taiwan
Wu, M.; Tan, H. N.; Lo, W. C.; Tsai, C. T.
The river upstream of watersheds in Taiwan is very steep, where soil and rock are often unstable so that the river watershed typically has the attribute of high sand yield and turbid runoff due to the excessive erosion in the heavy rainfall seasons. If flood water overflows the river bank, it would lead to a disaster in low-altitude plains. When flood retards or recesses, fine sediment would deposit. Over recent decades, many landslides arise in the Zengwen river watershed due to climate changes, earthquakes, and typhoons. The rocks and sands triggered by these landslides would move to the river channel through surface runoff, which may induce sediment disasters and also render an impact on the stability and sediment transport of the river channel. The risk of the sediment disaster could be reduced by implementing dredging works. However, because of the nature of the channel, the dredged river sections may have sediment depositions back; thus, causing an impact on flood safety. Therefore, it is necessary to evaluate the effectiveness of dredged works from the perspectives of hydraulic, sediment transport, and flood protection to achieve the objective of both disaster prevention and river bed stability. We applied the physiographic soil erosion-deposition (PSED) model to simulate the sediment yield, the runoff, and sediment transport rate of the Zengwen river watershed corresponding to one-day rainstorms of the return periods of 25, 50, and 100 year. The potential of sediment deposition and erosion in the river sections of the Zengwen river could be simulated by utilizing the alluvial river-movable bed two dimensional (ARMB-2D) model. The results reveal that the tendency for the potential of river sediment deposition and erosion obtained from these two models is agreeable. Furthermore, in order to evaluate the efficiency of sediment deposition reduction, two quantized values, the rate of sediment deposition reduction and the ratio of sediment deposition reduction
Innocuous oil as an additive for reductive reactions involving zero valence iron
International Nuclear Information System (INIS)
Cary, J.W.; Cantrell, K.J.
Reductive reactions involving zero valence iron appear to hold promise for in situ remediation of sites containing chlorinated hydrocarbon solvents and certain reducible metals and radionuclides. Treatment involves the injection of metallic iron and the creation of low levels of dissolved oxygen in the aqueous phase through oxidation of the metallic iron. The use of a biodegradable immiscible and innocuous organic liquid such as vegetable oil as an additive offers several intriguing possibilities. The oil phase creates a large oil-water interface that is immobile with respect to flow in the aqueous phase. This phase will act as a trap for chlorinated hydrocarbons and could potentially increase the reaction efficiency of reductive dehalogenation of chlorinated hydrocarbons by the metallic iron. When iron particles are suspended in the oil before injection they are preferentially held in the oil phase and tend to accumulate at the oil-water interface. Thus oil injection can serve as a mechanism for creating a stable porous curtain of metallic iron in the vadose to maintain a low oxygen environment which will minimize the consumption of the iron by molecular oxygen
Significance of iron reduction for the therapy of chronic hepatitis C
Directory of Open Access Journals (Sweden)
Nožić Darko
Full Text Available Background. It has been established that many patients with chronic hepatitis C have elevated serum iron, feritin levels and iron deposits in the liver. Therefore, the liver damage due to hepatitis C virus may be aggravated with iron overload. In many studies higher levels of iron in the blood and the liver were connected with the decreased response to interferon-alfa therapy for chronic viral hepatitis C. Recent introduction of pegylated interferons plus ribavirin has improved the therapeutic response, so it is now possible to cure more than 50% of the patients. Case report. Three patients with chronic hepatitis C and iron overload were presented. Iron reduction therapy using phlebotomy or eritrocytapheresis with plasmapheresis was done at different times in regard to specific antiviral therapy or as a sole therapy. Conclusion. It has been shown that iron reduction, sole or combined with antiviral therapy, led to the deacreased aminotransferase serum activity and might have slow down the evolution of chronic hepatitis C viral infection.
Effect of phosphorus addition on the reductive transformation of pentachlorophenol (PCP) and iron reduction with microorganism involvement.
Wang, Yongkui; Liu, Xianli; Huang, Jiexun; Xiao, Wensheng; Zhang, Jiaquan; Yin, Chunqin
The transformation of phosphorus added to the soil environment has been proven to be influenced by the Fe biochemical process, which thereby may affect the transformation of organic chlorinated contaminants. However, the amount of related literatures regarding this topic is limited. This study aimed to determine the effects of phosphorus addition on pentachlorophenol (PCP) anaerobic transformation, iron reduction, and paddy soil microbial community structure. Results showed that the transformation of phosphorus, iron, and PCP were closely related to the microorganisms. Moreover, phosphorus addition significantly influenced PCP transformation and iron reduction, which promoted and inhibited these processes at low and high concentrations, respectively. Both the maximum reaction rate of PCP transformation and the maximum Fe(II) amount produced were obtained at 1 mmol/L phosphorus concentration. Among the various phosphorus species, dissolved P and NaOH-P considerably changed, whereas only slight changes were observed for the remaining phosphorus species. Microbial community structure analysis demonstrated that adding low concentration of phosphorus promoted the growth of Clostridium bowmanii, Clostridium hungatei, and Clostridium intestinale and Pseudomonas veronii. By contrast, high-concentration phosphorus inhibited growth of these microorganisms, similar to the curves of PCP transformation and iron reduction. These observations indicated that Clostridium and P. veronii, especially Clostridium, played a vital role in the transformation of related substances in the system. All these findings may serve as a reference for the complicated reactions among the multiple components of soils.
Effect of Organic Substances on the Efficiency of Fe(Ii to Fe(Iii Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process
Directory of Open Access Journals (Sweden)
Krupińska Izabela
Full Text Available One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3. The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D. It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot], efficiency of Fe(II to Fe(III oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII when used as an oxidizing agent. The application of potassium manganate (VII for oxidation of Fe(II ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.
Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process
Krupińska, Izabela
One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.
Preparation of Metallic Iron Powder from Pyrite Cinder by Carbothermic Reduction and Magnetic Separation
Directory of Open Access Journals (Sweden)
Hongming Long
Full Text Available The reduction and magnetic separation procedure of pyrite cinder in the presence of a borax additive was performed for the preparation of reduced powder. The effects of borax dosage, reduction temperature, reduction time and grinding fineness were investigated. The results show that when pyrite cinder briquettes with 5% borax were pre-oxidized at 1050 °C for 10 min, and reduced at 1050 °C for 80 min, with the grinding fineness (<0.44 mm passing 81%, the iron recovery was 91.71% and the iron grade of the magnetic concentrate was 92.98%. In addition, the microstructures of the products were analyzed by optical microscope, scanning electron microscope (SEM, and mineralography, and the products were also studied by the X-ray powder diffraction technique (XRD to investigate the mechanism; the results show that the borax additive was approved as a good additive to improve the separation of iron and gangue.
Thermal conductivity enhancement and sedimentation reduction of magnetorheological fluids with nano-sized Cu and Al additives
Rahim, M. S. A.; Ismail, I.; Choi, S. B.; Azmi, W. H.; Aqida, S. N.
This work presents enhanced material characteristics of smart magnetorheological (MR) fluids by utilizing nano-sized metal particles. Especially, enhancement of thermal conductivity and reduction of sedimentation rate of MR fluids those are crucial properties for applications of MR fluids are focussed. In order to achieve this goal, a series of MR fluid samples are prepared using carbonyl iron particles (CIP) and hydraulic oil, and adding nano-sized particles of copper (Cu), aluminium (Al), and fumed silica (SiO2). Subsequently, the thermal conductivity is measured by the thermal property analyser and the sedimentation of MR fluids is measured using glass tubes without any excitation for a long time. The measured thermal conductivity is then compared with theoretical models such as Maxwell model at various CIP concentrations. In addition, in order to show the effectiveness of MR fluids synthesized in this work, the thermal conductivity of MRF-132DG which is commercially available is measured and compared with those of the prepared samples. It is observed that the thermal conductivity of the samples is much better than MRF-132DG showing the 148% increment with 40 vol% of the magnetic particles. It is also observed that the sedimentation rate of the prepared MR fluid samples is less than that of MRF-132DG showing 9% reduction with 40 vol% of the magnetic particles. The mixture optimized sample with high conductivity and low sedimentation was also obtained. The magnetization of the sample recorded an enhancement of 70.5% when compared to MRF-132DG. Furthermore, the shear yield stress of the sample were also increased with and without the influence of magnetic field.
(99)Tc(VII) Retardation, Reduction, and Redox Rate Scaling in Naturally Reduced Sediments.
Liu, Yuanyuan; Liu, Chongxuan; Kukkadapu, Ravi K; McKinley, James P; Zachara, John; Plymale, Andrew E; Miller, Micah D; Varga, Tamas; Resch, Charles T
An experimental and modeling study was conducted to investigate pertechnetate (Tc(VII)O4(-)) retardation, reduction, and rate scaling in three sediments from Ringold formation at U.S. Department of Energy's Hanford site, where (99)Tc is a major contaminant in groundwater. Tc(VII) was reduced in all the sediments in both batch reactors and diffusion columns, with a faster rate in a sediment containing a higher concentration of HCl-extractable Fe(II). Tc(VII) migration in the diffusion columns was reductively retarded with retardation degrees correlated with Tc(VII) reduction rates. The reduction rates were faster in the diffusion columns than those in the batch reactors, apparently influenced by the spatial distribution of redox-reactive minerals along transport paths that supplied Tc(VII). X-ray computed tomography and autoradiography were performed to identify the spatial locations of Tc(VII) reduction and transport paths in the sediments, and results generally confirmed the newly found behavior of reaction rate changes from batch to column. The results from this study implied that Tc(VII) migration can be reductively retarded at Hanford site with a retardation degree dependent on reactive Fe(II) content and its distribution in sediments. This study also demonstrated that an effective reaction rate may be faster in transport systems than that in well-mixed reactors.
Reductive debromination of polybrominated diphenyl ethers in anaerobic sediment and a biomimetic system.
Tokarz, John A; Ahn, Mi-Youn; Leng, June; Filley, Timothy R; Nies, Loring
Because of the bioaccumulation of penta- and tetrapolybrominated diphenyl ether (PBDE) flame retardants in biota,the environmental biotransformation of decabromodiphenyl ether (BDE-209) is of interest. BDE-209 accounts for more than 80% by mass of PBDE production and is the dominant PBDE in sediments. Most sediments are anaerobic and reports of microbial reductive dehalogenation of hydrophobic persistent organohalogen pollutants are numerous. Reductive debromination of BDE-209 in the environment could provide a significant source of lesser-brominated PBDEs to biota. Moreover, a recent study showed that BDE-209 debrominates in sewage sludge, and another demonstrated that some halorespiring bacteria will debrominate BDE-209. To determine whether reductive debromination of BDE-209 occurs in sediments, parallel experiments were conducted using anaerobic sediment microcosms and a cosolvent-enhanced biomimetic system. In the biomimetic system, reductive debromination occurred at rates corresponding to bromine substitution levels with a BDE-209 half-life of only 18 s compared with a halflife of almost 60 days for 2,2',4,4'-tetrabromodiphenyl ether. In sediment, the measured debromination half-life of BDE-209 was well over a decade and was in good agreement with the predicted value obtained from the biomimetic experiment. Product congeners were predominantly double para-substituted. BDE-209 debrominated in sediment with a corresponding increase in nona-, octa-, hepta-, and hexa-PBDEs. Nine new PBDE congeners appeared in sediment from reductive debromination. Given the very large BDE-209 burden already in sediments globally, it is important to determine whether this transformation is a significant source of lesser-brominated PBDEs to the environment.
Recovery of iron from cyanide tailings with reduction roasting–water leaching followed by magnetic separation
International Nuclear Information System (INIS)
Zhang, Yali; Li, Huaimei; Yu, Xianjin
Highlights: ► Using reduction roasting–water leaching–magnetic separation method, the recovery of iron from cyanide tailings was optimized. ► The recovery of iron was highly depended on the water-leaching process after reduction roasting. ► The results suggest that the method can be effectively used for iron recovery, and the grade of magnetic concentrate and recovery rate can reach 59.11% and 75.12%, respectively. - Abstract: Cyanide tailing is a kind of solid waste produced in the process of gold extraction from gold ore. In this paper, recovery of iron from cyanide tailings was studied with reduction roasting–water leaching process followed by magnetic separation. After analysis of chemical composition and crystalline phase, the effects of different parameters on recovery of iron were chiefly introduced. Systematic studies indicate that the high recovery rate and grade of magnetic concentrate of iron can be achieved under the following conditions: weight ratios of cyanide tailings/activated carbon/sodium carbonate/sodium sulfate, 100:10:3:10; temperature, 50 °C; time, 60 min at the reduction roasting stage; the liquid to solid ratio is 15:1 (ml/g), leaching at 60 °C for 5 min and stirring speed at 20 r/min at water-leaching; exciting current is 2 A at magnetic separation. The iron grade of magnetic concentrate was 59.11% and the recovery ratio was 75.12%. The mineralography of cyanide tailings, roasted product, water-leached sample, magnetic concentrate and magnetic tailings were studied by X-ray powder diffraction (XRD) technique. The microstructures of above products except magnetic tailings were also analyzed by scanning electron microscope (SEM) and energy disperse spectroscopy (EDS) to help understand the mechanism.
Mössbauer spectroscopic studies on the iron forms of deep-sea sediments
Drodt, M.; Trautwein, A. X.; König, I.; Suess, E.; Koch, C. Bender
Mössbauer spectroscopy was applied to characterize the valence states Fe(II) and Fe(III) in sedimentary minerals from a core of the Peru Basin. The procedure in unraveling this information includes temperature-dependent measurements from 275 K to very low temperature (300 mK) in zero-field and also at 4.2 K in an applied field (up to 6.2 T) and by mathematical procedures (least-squares fits and spectral simulations) in order to resolve individual spectral components. The depth distribution of the amount of Fe(II) is about 11% of the total Fe to a depth of 19 cm with a subsequent steep increase (within 3 cm) to about 37%, after which it remains constant to the lower end of the sediment core (at about 40 cm). The steep increase of the amount of Fe(II) defines a redox boundary which coincides with the position where the tan/green color transition of the sediment occurs. The isomer shifts and quadrupole splittings of Fe(II) and Fe(III) in the sediment are consistent with hexacoordination by oxygen or hydroxide ligands as in oxide and silicate minerals. Goethite and traces of hematite are observed only above the redox boundary, with a linear gradient extending from about 20% of the total Fe close to the sediment surface to about zero at the redox boundary. The superparamagnetic relaxation behavior allows to estimate the order of magnitude for the size of the largest goethite and hematite particles within the particle-site distribution, e.g. 170 Å and 50 Å, respectively. The composition of the sediment spectra recorded at 300 mK in zero-field, apart from the contributions due to goethite and hematite, resembles that of the sheet silicates smectite, illite and chlorite, which have been identified as major constituents of the sediment in the clay-mineral iron is redox sensitive. It is proposed that the color change of the sediment at the redox boundary from tan to green is related to the increase of Fe(II)-Fe(III) pairs in the layer silicates, because of the
Sulfur and Iron Cycling in a Coastal Sediment - Radiotracer Studies and Seasonal Dynamics
DEFF Research Database (Denmark)
to 2 mm in the oxidized surface layer of the sediment. The radiotracer data were analyzed by a mathematical model which showed that, due to partial, rapid reoxidation of radioactive sulfide during incubation, the actual reduction rates in this layer were probably underestimated 5-fold. In the deeper......, sulfidic zone, measured rates appeared to be correct. Sulfate reduction followed the seasonal variation in temperature with maximum activity at 1-2 cm depth in late summer. In spite of its rapid production, free H2S was detectable in the porewater only below the depth of free Fe2+ at 6-7 cm throughout...
Surface carbon influences on the reductive transformation of TCE in the presence of granular iron.
Firdous, R; Devlin, J F
To gain insight into the processes of transformations in zero-valent iron systems, electrolytic iron (EI) has been used as a surrogate for the commercial products actually used in barriers. This substitution facilitates mechanistic studies, but may not be fully representative of all the relevant processes at work in groundwater remediation. To address this concern, the kinetic iron model (KIM) was used to investigate sorption and reactivity differences between EI and Connelly brand GI, using TCE as a probe compound. It was observed that retardation factors (R app ) for GI varied non-linearly with influent concentrations to the columns (C o ), and declined significantly as GI aged. In contrast, R app values for EI were small and insensitive to C o , and changed minimally with iron aging. Moreover, although declines in the rate constants (k) and increases in the sorption coefficients were observed for both iron types, they were most pronounced in the case of EI. SEM scans of the EI surface before and after aging (90 days) established the appearance of carbon on the older surface. This work provides evidence that iron with a higher surface carbon content outperforms pure iron, suggesting that the carbon is actively involved in promoting TCE reduction. Copyright © 2017 Elsevier B.V. All rights reserved.
Screening the performance of lubricants for ironing of stainless steel with a strip reduction test
DEFF Research Database (Denmark)
Andreasen, Jan Lasson; Bay, Niels; Andersen, Mette Merete
A laboratory strip reduction test simulating the tribological conditions of an ironing process is proposed. The test is capable of simulating varying process conditions such as reduction, drawing speed, tool temperature and sliding length. The test makes it possible to quantify the onset of break...... of breakdown of the lubricant film and subsequent galling. Experimental investigations of stainless steel show the influence of varying process conditions and the performance of different lubricants.......A laboratory strip reduction test simulating the tribological conditions of an ironing process is proposed. The test is capable of simulating varying process conditions such as reduction, drawing speed, tool temperature and sliding length. The test makes it possible to quantify the onset...
Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer
Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.
weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.
Controlled electropolymerisation of a carbazole-functionalised iron porphyrin electrocatalyst for CO2 reduction
DEFF Research Database (Denmark)
Hu, Xinming; Salmi, Zakaria; Lillethorup, Mie
Using a one-step electropolymerisation procedure, CO2 absorbing microporous carbazole-functionalised films of iron porphyrins are prepared in a controlled manner. The electrocatalytic reduction of CO2 for these films is investigated to elucidate their efficiency and the origin of their ultimate...
Potentiometric assessment of iron release during ferritin reduction by exogenous agents.
Vladimirova, Lilia S; Kochev, Valery K
This work studied the possibilities for quantitative determination of iron mobilization in connection with ferritin reduction by ascorbic acid (vitamin C) and sodium dithionite in vitro. The iron storage protein was incubated with an excess of reductant in aerobic conditions in the absence of complexing agents in the medium. The release of Fe(2+) was let to go to completion, and the overall content of Fe(2+) in the solution was evaluated with the aid of potentiometric titration using Ce(4+) as an oxidizing titrant. Results suggest a moderate iron efflux under the influence of the chosen reducing agents. Although such a reduction of the protein mineral core by dihydroxyfumarate contributes greatly to the iron mobilization, ferritin behavior with vitamin C and dithionite seems to be different. Although redox properties of dihydroxyfumarate are determined by hydroxyl groups similar to those of ascorbic acid, the two compounds differ significantly in structure, and this could be the basis for an explanation of the specificities in their interaction with ferritin. As revealed by the study, potentiometric titration promises to be a reliable tool for evaluation of the amount of Fe(2+) present in the solution as a result of the reduction of the ferritin's mineral core. 2010 Elsevier Inc. All rights reserved.
Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization
International Nuclear Information System (INIS)
Neri, G.; Visco, A.M.; Galvagno, S.; Donato, A.; Panzalorto, M.
Gold on iron oxides catalysts have been characterized by temperature programmed reduction (TPR) and X-ray diffraction spectroscopy (XRD). The influence of preparation method, gold loading and pretreatment conditions on the reducibility of iron oxides have been investigated. On the impregnated Au/iron oxide catalysts as well as on the support alone the partial reduction of Fe(III) oxy(hydroxides) to Fe 3 O 4 starts in the 550 and 700 K temperature range. On the coprecipitated samples, the temperature of formation of Fe 3 O 4 is strongly dependent on the presence of gold. The reduction temperature is lowered as the gold loading is increased. The reduction of Fe 3 O 4 to FeO occurs at about 900 K and is not dependent on the presence of gold and the preparation method. It is suggested that the effect of gold on the reducibility of the iron oxides is related to an increase of the structural defects and/or of the surface hydroxyl groups. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)
Bacterial communities potentially involved in iron-cycling in Baltic Sea and North Sea sediments revealed by pyrosequencing
DEFF Research Database (Denmark)
Reyes, Carlen; Dellwig, Olaf; Dähnke, K.
To gain insight into the bacterial communities involved in iron-(Fe) cycling under marine conditions, we analysed sediments with Fe-contents (0.5-1.5 wt %) from the suboxic zone at a marine site in the Skagerrak (SK) and a brackish site in the Bothnian Bay (BB) using 16S rRNA gene pyrosequencing....
Impact of Sediment-Bound Iron on Redox Buffering in a Landfill Leachate Polluted Aquifer (Vejen, Denmark)
DEFF Research Database (Denmark)
Heron, Gorm; Christensen, Thomas Højlund
Sediments sampled along a central flow line of the leachate pollution plume at the Vejen Landfill, Denmark, were characterized in detail with respect to the forms and pools of Fe(ll) and Fe(lll). After 15 yr of leaching, redox reactions had diminished the pool of iron(ll1) oxides and hydroxides...
Mud, models, and managers: Reaching consensus on a watershed strategy for sediment load reduction
Wilcock, P. R.; Cho, S. J.; Gran, K.; Belmont, P.; Hobbs, B. F.; Heitkamp, B.; Marr, J. D.
Agricultural nonpoint source sediment pollution is a leading cause of impairment of U.S. waters. Sediment sources are often on private land, such that solutions require not only considerable investment, but broad acceptance among landowners. We present the story of a participatory modeling exercise whose goal was to develop a consensus strategy for reducing sediment loading from the Greater Blue Earth River Basin, a large (9,200 km2) watershed in southern Minnesota dominated by row crop agriculture. The Collaborative for Sediment Source Reduction was a stakeholder group of farmers, industry representatives, conservation groups, and regulatory agencies. We used a participatory modeling approach to promote understanding of the problem, to define the scope of solutions acceptable to farmers, to develop confidence in a watershed model, and to reach consensus on a watershed strategy. We found that no existing watershed model could provide a reliable estimate of sediment response to management actions and developed a purpose-built model that could provide reliable, transparent, and fast answers. Because increased stream flow was identified as an important driver of sediment loading, the model and solutions included both hydrologic and sediment transport components. The model was based on an annual sediment budget with management actions serving to proportionally reduce both sediment sources and sediment delivery. Importantly, the model was developed in collaboration with stakeholders, such that a shared understanding emerged regarding of the modeling challenges and the reliability of information used to strongly constrain model output. The simplicity of the modeling approach supported stakeholder engagement and understanding, thereby lowering the social barrier between expert modeler and concerned stakeholder. The consensus strategy focused on water storage higher in the watershed in order to reduce river discharge and the large supply of sediment from near
Obligatory reduction of ferric chelates in iron uptake by soybeans.
Chaney, R L; Brown, J C; Tiffin, L O
The contrasting Fe(2+) and Fe(3+) chelating properties of the synthetic chelators ethylenediaminedi (o-hydroxyphenylacetate) (EDDHA) and 4,7-di(4-phenylsulfonate)-1, 10-phenanthroline (bathophenanthrolinedisulfonate) (BPDS) were used to determine the valence form of Fe absorbed by soybean roots supplied with Fe(3+)-chelates. EDDHA binds Fe(3+) strongly, but Fe(2+) weakly; BPDS binds Fe(2+) strongly but Fe(3+) weakly. Addition of an excess of BPDS to nutrient solutions containing Fe(3+)-chelates inhibited soybean Fe uptake-translocation by 99+%; [Fe(II) (BPDS)(3)](4-) accumulated in the nutrient solution. The addition of EDDHA caused little or no inhibition. These results were observed with topped and intact soybeans. Thus, separation and absorption of Fe from Fe(3+)-chelates appear to require reduction of Fe(3+)-chelate to Fe(2+)-chelate at the root, with Fe(2+) being the principal form of Fe absorbed by soybean.
Influence of plants on the reduction of hexavalent chromium in wetland sediments
Energy Technology Data Exchange (ETDEWEB)
Zazo, Juan A. [Department of Chemical Engineering, Universidad Autonoma de Madrid, Madrid, 28049 (Spain)], E-mail: email@example.com; Paull, Jeffery S.; Jaffe, Peter R. [Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ 08544 (United States)
This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles. - The presence of plants enhances the reduction of Cr(VI) in wetland sediments by modifying the governing biogeochemical cycle.
Studies of iron in deep-sea sediments by Moessbauer spectroscopy
International Nuclear Information System (INIS)
Drodt, M.; Lougear, A.; Trautwein, A.X.; Koenig, I.; Suess, E.; Koch, C. Bender
The distribution of the forms of Fe in the solid phases in core samples of sediments from the Peru Basin has been investigated by Moessbauer spectroscopy with special attention to the cause of the sharp color transition between an upper green colored and a lower tan colored part. An important part of sample handling includes strict exclusion of oxygen during preparation of absorbers and measurements at cryogenic temperatures. The measurement strategy includes measurements between 77 K and 300 mK in zero external magnetic field, supplemented by measurements in external magnetic fields at 4.2 and 300 mK (up to 6.2 and 1 T, respectively). The temperature scans allow detection, identification and quantification of superparamagnetic iron oxides (goethite and hematite). The oxides are only present in samples from the upper tan-colored part of the core. The major part of the Fe(II) and Fe(III) (>80%) is present in a magnetic structure similar to that of layer silicates. The relative Fe(II) content of the layer silicates is practically identical to that determined from the paramagnetic components measured at liquid nitrogen temperature. This shows that the color transition in the sediment coincides with a change in the relative Fe(II) content in layer silicates from 11 to 37%. The color change can thus be explained by an increase in occurrence of Fe(II)-Fe(III) pairs exhibiting absorption bands due to intervalence electron transfer
Ammonia from iron(II) reduction of nitrite and the Strecker synthesis: do iron(II) and cyanide interfere with each other?
Summers, D. P.; Lerner, N.
The question of whether the production of ammonia, from the reduction of nitrite by iron(II), is compatible with its use in the Strecker synthesis of amino acids, or whether the iron and the cyanide needed for the Strecker synthesis interfere with each other, is addressed. Results show that the presence of iron(II) appears to have little, or no, effect on the Strecker synthesis. The presence of cyanide does interfere with reduction of nitrite, but the reduction proceeds at cyanide/iron ratios of less than 4:1. At ratios of about 2:1 and less there is only a small effect. The reduction of nitrite and the Strecker can be combined to proceed in each other's presence, to yield glycine from a mixture of nitrite, Fe+2, formaldehyde, and cyanide.
The development of a laterally confined laboratory fan delta under sediment supply reduction
Zhang, Xiaofeng; Wang, Siqiang; Wu, Xi; Xu, Shun; Li, Zhangyong
In previous fan delta experiments, the effect of lateral confinement was generally ignored as these fans were usually unconfined with semiconical geometries. However, in gorge areas, fan development is usually laterally confined by valley walls. This study investigates autogenic processes of fan deltas in a laterally confined experimental tank. The experiment is divided into three phases. The sediment supply is held constant within each phase, so the autogenic processes of the fan are separated from the allogenic forcings. Results indicate that laterally confined fan deltas have higher progradation and aggradation potential, more regular channel braiding, and more even transverse sedimentation than unconfined fans. Besides, responses of fan deltas to sediment supply reduction are investigated in this research. At the initiation of the second and third phases, sediment feed rates are instantaneously reduced so that the allogenic forcings are predominant. Observations show that under sediment supply reduction, channelization on fan deltas are more pronounced and durations of the fluvial cycles are longer. The adjustment of fan morphology becomes slower as the self-regulation capacity of the fan decreases with reduced sediment supply.
Fundamentals of fast reduction of ultrafine iron ore at low temperature
Institute of Scientific and Technical Information of China (English)
Pei Zhao; Peimin Guo
Fundamentals on the fast reduction of ultrafine iron ore at low temperature, including characterization of ultrafine ore, de- oxidation thermodynamics of stored-energy ultrafine ore, kinetics of iron ore deoxidation, and deoxidation mechanism, etc., and a new ironmaking process are presented in this article. Ultrafine ore concentrate with a high amount of stored energy can be produced by mechanical milling, and can be dcoxidated fast below 700℃ by either the coal-based or gas-based process. This novel process has some advantages over others: high productivity, low energy consumption, and environmental friendliness.
Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...
Enhancing the Process of Anaerobic Ammonium Oxidation Coupled to Iron Reduction in Constructed Wetland Mesocosms with Supplementation of Ferric Iron Hydroxides
Shuai, W.; Jaffe, P. R.
Effective ammonium (NH4+) removal has been a challenge in wastewater treatment processes. Aeration, which is required for the conventional NH4+ removal approach by ammonium oxidizing bacteria, is an energy intensive process during the operation of wastewater treatment plant. The efficiency of NH4+ oxidation in natural systems is also limited by oxygen transfer in water and sediments. The objective of this study is to enhance NH4+ removal by applying a novel microbial process, anaerobic NH4+ oxidation coupled to iron (Fe) reduction (also known as Feammox), in constructed wetlands (CW). Our studies have shown that an Acidimicrobiaceae bacterium named A6 can carry out the Feammox process using ferric Fe (Fe(III)) minerals like ferrihydrite as their electron acceptor. To investigate the properties of the Feammox process in CW as well as the influence of electrodes, Feammox bacterium A6 was inoculated in planted CW mesocosms with electrodes installed at multiple depths. CW mesocosms were operated using high NH4+ nutrient solution as inflow under high or low sediment Fe(III) level. During the operation, NH4+ and ferrous Fe concentration, pore water pH, voltages between electrodes, oxidation reduction potential and dissolved oxygen were measured. At the end of the experiment, CW sediment samples at different depths were taken, DNAs were extracted and quantitative polymerase chain reaction and pyrosequencing were performed to analyze the microbial communities. The results show that the high Fe level CW mesocosm has much higher NH4+ removal ability than the low Fe level CW mesocosm after Fe-reducing conditions are developed. This indicates the enhanced NH4+ removal can be attributed to elevated Feammox activity in high Fe level CW mesocosm. The microbial community structures are different in high or low Fe level CW mesocosms and on or away from the installed electrodes. The voltages between cathode and anode increased after the injection of A6 enrichment culture in low Fe
Research on CO2 Emission Reduction Mechanism of China's Iron and Steel Industry under Various Emission Reduction Policies
Directory of Open Access Journals (Sweden)
Ye Duan
Full Text Available In this paper, a two-stage dynamic game model of China's iron and steel industry is constructed. Carbon tax levy, product subsidy, carbon capture and sequestration (CCS and other factors are included in the emission reduction mechanism. The effects of emissions reduction and the economic impact of China's overall steel industry (and that of its six main regions are investigated for the first time under different scenarios. As new findings, we report the following: (1 Not all factors declined. The overall social welfare, consumer surplus, output and emissions decrease with a gradual increase in the reduction target, whereas the carbon tax value, unit value of product subsidies and total subsidies show a rising trend; (2 A combination of multiple emissions reduction policies is more effective than a single policy. With the implementation of a combined policy, regional output polarization has eased; (3 Steel output does not exceed 950 million tons, far below the current peak. These results will help the industry to formulate reasonable emissions reduction and output targets. In short, in effort to eliminate industry poverty and to alleviate overcapacity, the industry should not only adopt the various coordinated reduction policies, but also fully consider regional differences and reduction needs.
Application of natural gas to the direct reduction of iron ore
Energy Technology Data Exchange (ETDEWEB)
The Gas Committee of the U.N. Economic Commission for Europe evaluated the potentials of natural gas for direct reduction of iron ore. The report, based essentially on that by the Italian representative E. Pasero with comments and observations from experts of the other member countries, indicated the general tendency of the iron and steel industry to use natural gas to reduce production costs by reducing coke consumption. By the end of 1972, gas consumption by these industries was reported at 38.8 billion Btu/ton (10.79 Gcal/m ton) by the Steel Committee of the U.N. Economic Commission at the symposium on the economic and technical aspects of the direct reduction of iron ore, held in September 1972 in Bucharest. In comparison, coke consumption was 9.5 billion Btu/ton (2.64 Gcal/m ton) steel, liquid hydrocarbons 3.1 billion Btu (0.85 Gcal), and electricity 16.1 billion Btu (4.46 Gcal). Natural gas was used mainly for ore reduction and generation of the reducing gas in-shaft furnaces with backdraft heating circulation, fixed-bed furances (Hyl type), and fluidized-bed reactors. Processes include the Midrex (shaft furnace), H.I.B. (fluidized bed), and Novalfer (fluidized bed). These processes are used to obtain 4.5 million tons/yr of iron sponge for the production of steel in electric furnaces. The natural gas outlook for direct reduction of iron will depend on local conditions and fuel availability. Its industrial application has been most successful in mini-steel installations, especially in the U.S., Japan, and Western Europe, and it is recommended for developing countries with no steel-industry basis.
Nanoscale zero-valent iron (nZVI) synthesis in a Mg-aminoclay solution exhibits increased stability and reactivity for reductive decontamination
DEFF Research Database (Denmark)
Hwang, Yuhoon; Lee, Young-Chul; Mines, Paul D.
Nanoscale zero-valent iron (nZVI) has often been explored as a reductant for detoxification of pollutants in environmental clean-ups. Despite the large surface area and superior reactivity of nZVI, its limited stability is a major obstacle in applying nZVI for in situ subsurface remediation, e......ZVI particles with higher crystallinity were produced. Stability of nZVI particles were evaluated using a sedimentation test and a dynamic light scattering technique. The characteristic time increased from 6.71 to 83.8 min, and particle (aggregate diameter) size decreased from 5132 to 186 nm with increasing...
Studies of Actinides Reduction on Iron Surfaces by Means of Resonant Inelastic X-ray Scattering
International Nuclear Information System (INIS)
Kvashnina, K.O.; Butorin, S.M.; Shuh, D.K.; Ollila, K.; Soroka, I.; Guo, J.-H.; Werme, L.; Nordgren, J.
The interaction of actinides with corroded iron surfaces was studied using resonant inelastic x-ray scattering (RIXS) spectroscopy at actinide 5d edges. RIXS profiles, corresponding to the f-f excitations are found to be very sensitive to the chemical states of actinides in different systems. Our results clearly indicate that U(VI) (as soluble uranyl ion) was reduced to U(IV) in the form of relatively insoluble uranium species, indicating that the iron presence significantly affects the mobility of actinides, creating reducing conditions. Also Np(V) and Pu (VI) in the ground water solution were getting reduced by the iron surface to Np(IV) and Pu (IV) respectively. Studying the reduction of actinides compounds will have an important process controlling the environmental behavior. Using RIXS we have shown that actinides, formed by radiolysis of water in the disposal canister, are likely to be reduced on the inset corrosion products and prevent release from the canister
Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst
Zelenay, Piotr; Wu, Gang
A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.
Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance
International Nuclear Information System (INIS)
Qi, B.; Andrew, J. S.; Arnold, D. P.
This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe_6_6Co_3_4) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe_2O_4) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.
Calcium-assisted reduction of cobalt ferrite nanoparticles for nanostructured iron cobalt with enhanced magnetic performance
Energy Technology Data Exchange (ETDEWEB)
Qi, B. [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States); Andrew, J. S. [University of Florida, Department of Materials Science and Engineering (United States); Arnold, D. P., E-mail: firstname.lastname@example.com [University of Florida, Interdisciplinary Microsystems Group, Department of Electrical and Computer Engineering (United States)
This paper demonstrates the potential of a calcium-assisted reduction process for synthesizing fine-grain (~100 nm) metal alloys from metal oxide nanoparticles. To demonstrate the process, an iron cobalt alloy (Fe{sub 66}Co{sub 34}) is obtained by hydrogen annealing 7-nm cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles in the presence of calcium granules. The calcium serves as a strong reducing agent, promoting the phase transition from cobalt ferrite to a metallic iron cobalt alloy, while maintaining high crystallinity. Magnetic measurements demonstrate the annealing temperature is the dominant factor of tuning the grain size and magnetic properties. Annealing at 700 °C for 1 h maximizes the magnetic saturation, up to 2.4 T (235 emu/g), which matches that of bulk iron cobalt.
In situ reduction of as-prepared γ-Iron Oxide Nanoparticles
DEFF Research Database (Denmark)
Garbus, Pelle Gorm; Ahlburg, Jakob; Christensen, Mogens
-ray diffraction measurement. The as-prepared maghemite nanoparticles were synthesized by the continuous decomposition of solutes in supercritical hydrothermal flow synthesis [3, 4]. The reagent used was ferric ammonium citrate (C6H8O7•xFe(III)•yNH3) that under hydrothermal flow synthesis decomposes into the γ......-iron oxide Fe2O3. The reduction of maghemite to body centered cubic (BCC) iron does not go through a detectable intermediate state.1.Jensen, K.M., et al., Mechanisms for iron oxide formation under hydrothermal conditions: an in situ total scattering study. ACS nano, 2014. 8(10): p. 10704-10714.2.Andersen, H...
Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron
International Nuclear Information System (INIS)
Liu, C.-C.; Tseng, D.-H.; Wang, C.-Y.
The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite (γ-Fe 2 O 3 ) to the more hydrated goethite (α-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe 3 O 4 ), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe 0 -TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE
Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron
Energy Technology Data Exchange (ETDEWEB)
Liu, C.-C. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China); Tseng, D.-H. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China)]. E-mail: firstname.lastname@example.com; Wang, C.-Y. [Graduate Institute of Environmental Engineering, National Central University, Chungli, Taiwan 32001 (China)
The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite ({gamma}-Fe{sub 2}O{sub 3}) to the more hydrated goethite ({alpha}-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe{sub 3}O{sub 4}), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe{sup 0}-TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE.
Nitrogen loss from anaerobic ammonium oxidation coupled to Iron(III) reduction in a riparian zone.
Ding, Bangjing; Li, Zhengkui; Qin, Yunbin
Anaerobic ammonium oxidation coupled to iron(III) reduction (termed Feammox) is a recently discovered pathway of nitrogen cycling. However, little is known about the pathways of N transformation via Feammox process in riparian zones. In this study, evidence for Feammox in riparian zones with or without vegetation cover was demonstrated using isotope tracing technique and high-throughput sequencing technology. The results showed that Feammox could occur in riparian zones, and demonstrated that N 2 directly from Feammox was dominant Feammox pathway. The Feammox rates in vegetated soil samples was 0.32-0.37 mg N kg -1 d -1 , which is higher than that in un-vegetated soil samples (0.20 mg N kg -1 d -1 ). Moreover, the growth of vegetation led to a 4.99-6.41% increase in the abundance of iron reducing bacteria (Anaeromyxobacter, Pseudomonas and Geobacter) and iron reducing bacteria play an essential role in Feammox process. An estimated loss of 23.7-43.9 kg N ha -1 year -1 was associated with Feammox in the examined riparian zone. Overall, the co-occurrence of ammonium oxidation and iron reduction suggest that Feammox can play an essential role in the pathway of nitrogen removal in riparian zones. Copyright © 2017 Elsevier Ltd. All rights reserved.
Reduction of ferric iron by acidophilic heterotrophic bacteria: evidence for constitutive and inducible enzyme systems in Acidiphilium spp.
Johnson, D B; Bridge, T A M
To compare the abilities of two obligately acidophilic heterotrophic bacteria, Acidiphilium acidophilum and Acidiphilium SJH, to reduce ferric iron to ferrous when grown under different culture conditions. Bacteria were grown in batch culture, under different aeration status, and in the presence of either ferrous or ferric iron. The specific rates of ferric iron reduction by fermenter-grown Acidiphilium SJH were unaffected by dissolved oxygen (DO) concentrations, while iron reduction by A. acidophilum was highly dependent on DO concentrations in the growth media. The ionic form of iron present (ferrous or ferric) had a minimal effect on the abilities of harvested cells to reduce ferric iron. Whole cell protein profiles of Acidiphilium SJH were very similar, regardless of the DO status of the growth medium, while additional proteins were present in A. acidophilum grown microaerobically compared with aerobically-grown cells. The dissimilatory reduction of ferric iron is constitutive in Acidiphilium SJH while it is inducible in A. acidophilum. Ferric iron reduction by Acidiphilium spp. may occur in oxygen-containing as well as anoxic acidic environments. This will detract from the effectiveness of bioremediation systems where removal of iron from polluted waters is mediated via oxidation and precipitation of the metal.
Methane production, sulfate reduction and competition for substrates in the sediments of Lake Washington
Energy Technology Data Exchange (ETDEWEB)
Kuivila, K.M.; Murray, J.W.; Devol, A.H. (Univ. of Washington, Seattle (USA)); Novelli, P.C. (Univ. of Colorado, Boulder (USA))
Rates of methane production (both acetate fermentation and CO{sub 2} reduction) and sulfate reduction were directly measured as a function of depth in the sediments of Lake Washington. Although methanogenesis was the primary mode of anaerobic respiration (63%), the major zone of methane production existed only below the sulfate reduction zone (16 cm). Acetate fermentation accounted for 61 to 85% of the total methane production, which is consistent with other low sulfate environments. The observed spatial separation of methane production and sulfate reduction, which has been reported for marine sediments, is attributed to competition between the methane-producing and sulfate-reducing bacteria for acetate and hydrogen. This hypothesis is supported by the strong correlation between the measured distributions of acetate and hydrogen and the rates of methane produced from these two precursors in Lake Washington sediments. Acetate concentrations increased rapidly (from 10-16 {mu}M to 30-40 {mu}M) once the sulfate concentration decreased below 30 {mu}M and methane production via acetate fermentation began. A similar trend was observed for hydrogen concentrations, which increased from 7 to 22 nM up to 40 to 55 nM, at the onset of methanogenesis from CO{sub 2} and H{sub 2} (sulfate concentrations of 35-40 {mu}M). These results show, for the first time in a freshwater lake, the separation of methane production and sulfate reduction and the corresponding changes in acetate and hydrogen concentrations.
Reduction of body iron in HFE-related haemochromatosis and moderate iron overload (Mi-Iron): a multicentre, participant-blinded, randomised controlled trial.
Ong, Sim Y; Gurrin, Lyle C; Dolling, Lara; Dixon, Jeanette; Nicoll, Amanda J; Wolthuizen, Michelle; Wood, Erica M; Anderson, Gregory J; Ramm, Grant A; Allen, Katrina J; Olynyk, John K; Crawford, Darrell; Ramm, Louise E; Gow, Paul; Durrant, Simon; Powell, Lawrie W; Delatycki, Martin B
The iron overload disorder hereditary haemochromatosis is most commonly caused by HFE p.Cys282Tyr homozygosity. In the absence of results from any randomised trials, current evidence is insufficient to determine whether individuals with hereditary haemochromatosis and moderately elevated serum ferritin, should undergo iron reduction treatment. This trial aimed to establish whether serum ferritin normalisation in this population improved symptoms and surrogate biomarkers. This study was a multicentre, participant-blinded, randomised controlled trial done at three centres in Australia. We enrolled people who were homozygous for HFE p.Cys282Tyr, aged between 18 and 70 years, with moderately elevated serum ferritin, defined as 300-1000 μg/L, and raised transferrin saturation. Participants were randomly assigned, via a computer-generated random number, to undergo either iron reduction by erythrocytapheresis (treatment group) or sham treatment by plasmapheresis (control group). Randomisation was stratified by baseline serum ferritin (cognitive subcomponent (-3·6, -5·9 to -1·3, p=0·0030), but not in the physical (-1·90 -4·5 to 0·63, p=0·14) and psychosocial (-0·54, -1·2 to 0·11, p=0·10) subcomponents. No serious adverse events occurred in either group. One participant in the control group had a vasovagal event and 17 participants (14 in the treatment group and three in the control group) had transient symptoms assessed as related to hypovolaemia. Mild citrate reactions were more common in the treatment group (32 events [25%] in 129 procedures) compared with the control group (one event [1%] in 93 procedures). To our knowledge, this study is the first to objectively assess the consequences of iron removal in individuals with hereditary haemochromatosis and moderately elevated serum ferritin. Our results suggest that serum ferritin normalisation by iron depletion could be of benefit for all individuals with hereditary haemochromatosis and elevated serum
Reductive debromination of decabromodiphenyl ether (BDE 209) by anaerobic sediment microorganisms
Energy Technology Data Exchange (ETDEWEB)
Parsons, J.; Zegers, B.; Skoczynska, E.; Voogt, P. de [IBED-Environmental Chemistry, Univ. of Amsterdam (Netherlands)
The environmental fate and effects of brominated flame retardants have been receiving increasing interest. Because of their high hydrophobicity, polybrominated diphenyl ether (PBDE) flame retardants in the aquatic environment are mainly present in sediments and biota. The long-term fate of these compounds will to a large extent depend on the potential for microbial degradation in sediments. Dehalogenation in anaerobic sediments has been found for many chlorinated aromatic compounds such as PCBs and PCDDs. Although there is little information available on the microbial degradation of PBDEs, there are reports showing that polybrominated biphenyls are readily debrominated in anaerobic sediments. Complete debromination of PBDEs in marine sediments may be an important route by which these compounds are removed from the marine environment. On the other hand, incomplete debromination may lead to the accumulation of PBDE congeners that are more bioavailable and more readily taken up by marine organisms. Recent reports indicate that BDE 209 is debrominated in the gut of carp. In this study we investigated the potential for reductive debromination of BDE 209 in anaerobic sediment suspensions.
PCB dechlorination hotspots and reductive dehalogenase genes in sediments from a contaminated wastewater lagoon.
Mattes, Timothy E; Ewald, Jessica M; Liang, Yi; Martinez, Andres; Awad, Andrew; Richards, Patrick; Hornbuckle, Keri C; Schnoor, Jerald L
Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that are distributed worldwide. Although industrial PCB production has stopped, legacy contamination can be traced to several different commercial mixtures (e.g., Aroclors in the USA). Despite their persistence, PCBs are subject to naturally occurring biodegradation processes, although the microbes and enzymes involved are poorly understood. The biodegradation potential of PCB-contaminated sediments in a wastewater lagoon located in Virginia (USA) was studied. Total PCB concentrations in sediments ranged from 6.34 to 12,700 mg/kg. PCB congener profiles in sediment sample were similar to Aroclor 1248; however, PCB congener profiles at several locations showed evidence of dechlorination. The sediment microbial community structure varied among samples but was dominated by Proteobacteria and Firmicutes. The relative abundance of putative dechlorinating Chloroflexi (including Dehalococcoides sp.) was 0.01-0.19% among the sediment samples, with Dehalococcoides sp. representing 0.6-14.8% of this group. Other possible PCB dechlorinators present included the Clostridia and the Geobacteraceae. A PCR survey for potential PCB reductive dehalogenase genes (RDases) yielded 11 sequences related to RDase genes in PCB-respiring Dehalococcoides mccartyi strain CG5 and PCB-dechlorinating D. mccartyi strain CBDB1. This is the first study to retrieve potential PCB RDase genes from unenriched PCB-contaminated sediments.
Hydrologically mediated iron reduction/oxidation fluctuations and dissolved organic carbon exports in tidal wetlands
Guimond, J. A.; Seyfferth, A.; Michael, H. A.
Salt marshes are biogeochemical hotspots where large quantities of carbon are processed and stored. High primary productivity and deposition of carbon-laden sediment enable salt marsh soils to accumulate and store organic carbon. Conversely, salt marshes can laterally export carbon from the marsh platform to the tidal channel and eventually the ocean via tidal pumping. However, carbon export studies largely focus on tidal channels, missing key physical and biogeochemical mechanisms driving the mobilization of dissolved organic carbon (DOC) within the marsh platform and limiting our understanding of and ability to predict coastal carbon dynamics. We hypothesize that iron redox dynamics mediate the mobilization/immobilization of DOC in the top 30 cm of salt marsh sediment near tidal channels. The mobilized DOC can then diffuse into the flooded surface water or be advected to tidal channels. To elucidate DOC dynamics driven by iron redox cycles, we measured porewater DOC, Fe(II), total iron, total sulfate, pH, redox potential, and electrical conductivity (EC) beside the creek, at the marsh levee, and in the marsh interior in a mid-latitude tidal salt marsh in Dover, Delaware. Samples were collected at multiple tide stages during a spring and neap tide at depths of 5-75cm. Samples were also collected from the tidal channel. Continuous Eh measurements were made using in-situ electrodes. A prior study shows that DOC and Fe(II) concentrations vary spatially across the marsh. Redox conditions near the creek are affected by tidal oscillations. High tides saturate the soil and decrease redox potential, whereas at low tide, oxygen enters the sediment and increases the Eh. This pattern is always seen in the top 7-10cm of sediment, with more constant low Eh at depth. However, during neap tides, this signal penetrates deeper. Thus, between the creek and marsh levee, hydrology mediates redox conditions. Based on porewater chemistry, if DOC mobilization can be linked to redox
Bacterial Sulfate Reduction Above 100-Degrees-C in Deep-Sea Hydrothermal Vent Sediments
DEFF Research Database (Denmark)
-reducing bacteria was done in hot deep-sea sediments at the hydrothermal vents of the Guaymas Basin tectonic spreading center in the Gulf of California. Radiotracer studies revealed that sulfate reduction can occur at temperatures up to 110-degrees-C, with an optimum rate at 103-degrees to 106-degrees......-C. This observation expands the upper temperature limit of this process in deep-ocean sediments by 20-degrees-C and indicates the existence of an unknown groUp of hyperthermophilic bacteria with a potential importance for the biogeochemistry of sulfur above 100-degrees-C....
Sulfate reduction and methane oxidation activity below the sulfate-methane transition zone in Alaskan Beaufort Sea continental margin sediments: Implications for deep sulfur cycling
Treude, Tina; Krause, Stefan; Maltby, Johanna; Dale, Andrew W.; Coffin, Richard; Hamdan, Leila J.
Two ∼6 m long sediment cores were collected along the ∼300 m isobath on the Alaskan Beaufort Sea continental margin. Both cores showed distinct sulfate-methane transition zones (SMTZ) at 105 and 120 cm below seafloor (cmbsf). Sulfate was not completely depleted below the SMTZ but remained between 30 and 500 μM. Sulfate reduction and anaerobic oxidation of methane (AOM) determined by radiotracer incubations were active throughout the methanogenic zone. Although a mass balance could not explain the source of sulfate below the SMTZ, geochemical profiles and correlation network analyses of biotic and abiotic data suggest a cryptic sulfur cycle involving iron, manganese and barite. Inhibition experiments with molybdate and 2-bromoethanesulfonate (BES) indicated decoupling of sulfate reduction and AOM and competition between sulfate reducers and methanogens for substrates. While correlation network analyses predicted coupling of AOM to iron reduction, the addition of manganese or iron did not stimulate AOM. Since none of the classical archaeal anaerobic methanotrophs (ANME) were abundant, the involvement of unknown or unconventional phylotypes in AOM is conceivable. The resistance of AOM activity to inhibitors implies deviation from conventional enzymatic pathways. This work suggests that the classical redox cascade of electron acceptor utilization based on Gibbs energy yields does not always hold in diffusion-dominated systems, and instead biotic processes may be more strongly coupled to mineralogy.
Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.
Lovley, D R; Phillips, E J
A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.
Iron isotope constraints on arsenic release from Mekong Delta sediments, Cambodia
Matsumoto, T.; Yamaguchi, K. E.; Hirata, T.; Yamagata, Y.; Yamaguchi, A.; Abe, G.
Arsenic-contaminated groundwater is a world-wide environmental problem and threatens more than 100 million people living in delta areas of South, SE and East Asia. It is typically associated with reducing aquifers with organic-rich alluvial sediments, little thermal gradients, low sulfate concentrations, and slow flushing rates. Such conditions are typical for low-lying countries in Asian deltas; however, compared to Bangladesh, Cambodia has received far less attention. Upon reductive dissolution of Fe-(oxyhydr)oxides that adsorbed As, Fe and As are released into solution as dissolved Fe2+ and arsenate, respectively. Following the oxidation of dissolved Fe2+, newly-formed Fe-(oxyhydr)oxides adsorb As again. Thus, in anoxic waters, concentrations of As correlate with those of dissolved Fe2+. Fluctuating redox conditions in the aquifer are control As release, although inhibition of adsorption of arsenate and arsenite onto the Fe-(oxyhydr)oxides occurs when the concentrations of phosphate, bicarbonate, silicate, and/or organic matter become sufficiently high. Biogeochemical redox reactions of Fe result in significant isotope fractionation (e.g., Johnson et al., 2008). We hypothesized that magnitude of isotope fractionation of Fe in the aquifer sediments, reflecting repeated (incomplete) redox reactions of Fe, may be proportional to the amount of total As release. We aim to calibrate the As release from aquifer sediment by Fe isotope analysis. As a preliminary study, series of sediment samples were collected from the Mekong Delta, Cambodia, in September 2016. Based on measurements by XRF, ICP-AES and ICP-MS, concentrations of As varied significantly covering the range from 4.5 to 15.5 µg/g with a median value of 11 µg/g (higher than the average crustal value of 5 µg/g), and those of Fe is from 2.6 to 9.7 wt.% with a median value of 7.1 wt.%. Concentrations of As and Fe show positive correlation (R2 = 0.72), indicating an effective redox cycling of Fe and As as
Carbothermal Reduction of Iron Ore in Its Concentrate-Agricultural Waste Pellets
Directory of Open Access Journals (Sweden)
Zhulin Liu
Full Text Available Carbon-containing pellets were prepared with the carbonized product of agricultural wastes and iron concentrate, and an experimental study on the direct reduction was carried out. The experimental results demonstrated that carbon-containing pellets could be rapidly reduced at 1200 to 1300°C in 15 minutes, and the proper holding time at high temperature was 15 to 20 min. The degree of reduction gradually increased with temperature rising, and the appropriate temperature of reducing pellets was 1200°C. The weight loss rate and reduction degree of pellets increased with the rise of carbon proportion, and the relatively reasonable mole ratio of carbon to oxygen was 0.9. A higher content of carbon and an appropriate content of volatile matters in biomass char were beneficial to the reduction of pellets. The carbon-containing pellets could be reduced at high speeds in the air, but there was some reoxidization phenomenon.
Rapid sedimentation of iron oxyhydroxides in an active hydrothermal shallow semi-enclosed bay at Satsuma Iwo-Jima Island, Kagoshima, Japan
Kiyokawa, Shoichi; Ueshiba, Takuya
Hydrothermal activity is common in the fishing port of Nagahama Bay, a small semi-enclosed bay located on the southwest coast of Satsuma Iwo-Jima Island (38 km south of Kyushu Island, Japan). The bay contains red-brown iron oxyhydroxides and thick deposits of sediment. In this work, the high concentration and sedimentation rates of oxyhydroxide in this bay were studied and the sedimentary history was reconstructed. Since dredging work in 1998, a thickness of 1.0-1.5 m of iron oxyhydroxide-rich sediments has accumulated on the floor of the bay. To estimate the volume of iron oxyhydroxide sediments and the amount discharged from hydrothermal vents, sediment traps were operated for several years and 13 sedimentary core samples were collected to reconstruct the 10-year sedimentary history of Nagahama Bay. To confirm the timing of sedimentary events, the core data were compared with meteorological records obtained on the island, and the ages of characteristic key beds were thus identified. The sedimentation rate of iron oxyhydroxide mud was calculated, after correcting for sediment input from other sources. The sediments in the 13 cores from Nagahama Bay consist mainly of iron oxyhydroxide mud, three thick tephra beds, and a topmost thick sandy mud bed. Heavy rainfall events in 2000, 2001, 2002, and 2004-2005 coincide with tephra beds, which were reworked from Iwo-Dake ash deposits to form tephra-rich sediment. Strong typhoon events with gigantic waves transported outer-ocean-floor sediments and supplied quartz, cristobalite, tridymite, and albite sands to Nagahama Bay. These materials were redeposited together with bay sediments as the sandy mud bed. Based on the results from the sediment traps and cores, it is estimated that the iron oxyhydroxide mud accumulated in the bay at the relatively rapid rate of 33.3 cm/year (from traps) and 2.8-4.9 cm/year (from cores). The pore water contents within the sediment trap and core sediments are 73%-82% and 47%-67%, respectively
Manganese, Iron, and Sulfur Cycling in a Coastal Marine Sediment, Aarhus Bay, Denmark
DEFF Research Database (Denmark)
-scale measurements showed that it extended to the upper 0-2.5 mm during summer, when the zones of Mn and Fe reduction were compressed towards the surface. Most of the H2S produced precipitated as iron sulfides and S0 by reaction with Fe. Both Fe(III) and a nonsulfur-bound authigenic Fe(II) pool reacted efficiently...... of a diatom spring bloom caused distinct maxima in SRR and Mn2+ at 0.5-1 cm depth within two weeks. In autumn, the reactive Mn oxides were depleted due to a net release of Mn2+ to the water column. Thus, the Mn cycle extended significantly into the water column, while a constant Fe pool over the year suggests...
Bacterial assimilation reduction of iron in the treatment of non-metallics
Directory of Open Access Journals (Sweden)
Peter Malachovský
Full Text Available Natural non-metallics, including granitoide and quartz sands, often contain iron which decreases the whiteness of these raw materials. Insoluble Fe3+ in these samples could be reduced to soluble Fe2+ by bacteria of Bacillus spp. and Saccharomyces spp. The leaching effect, observed by the measurement of Fe2+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-metallics was increased during a visual comparison of samples before and after bioleaching but samples contain selected magnetic particles. A removal of iron as well as a release of iron minerals from silicate matrix should increase the effect of the magnetic separation and should give a product which is suitable for industrial applications.
Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron
International Nuclear Information System (INIS)
Fiuza, Antonio; Silva, Aurora; Carvalho, Goreti; Fuente, Antonio V. de la; Delerue-Matos, Cristina
Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power α which is the order of the chemical reaction occurring at surface. We assumed α = 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.
Concentrations and Fractionation of Carbon, Iron, Sulfur, Nitrogen and Phosphorus in Mangrove Sediments Along an Intertidal Gradient (Semi-Arid Climate, New Caledonia
Directory of Open Access Journals (Sweden)
Jonathan Deborde
Full Text Available In mangrove ecosystems, strong reciprocal interactions exist between plant and substrate. Under semi-arid climate, Rhizophora spp. are usually predominant, colonizing the seashore, and Avicennia marina develops at the edge of salt-flats, which is the highest zone in the intertidal range. Along this zonation, distribution and speciation of C, Fe, S, N, and P in sediments and pore-waters were investigated. From the land-side to the sea-side of the mangrove, sediments were characterized by I/ increase in: (i water content; (ii TOC; (iii mangrove-derived OM; II/ and decrease in: (i salinity; (ii redox; (iii pH; (iv solid Fe and solid P. Beneath Avicennia and Rhizophora, TS accumulated at depth, probably as a result of reduction of iron oxides and sulfate. The loss of total Fe observed towards the sea-side may be related to sulfur oxidation and to more intense tidal flushing of dissolved components. Except the organic forms, dissolved N and P concentrations were very low beneath Avicennia and Rhizophora stands, probably as a result of their uptake by the root systems. However, in the unvegetated salt-flat, NH4+ can accumulate in organic rich and anoxic layers. This study shows: (i the evolution of mangrove sediment biogeochemistry along the intertidal zone as a result of the different duration of tidal inundation and organic enrichment; and (ii the strong links between the distribution and speciation of the different elements.
Reductive dehalogenation activity of indigenous microorganism in sediments of the Hackensack River, New Jersey.
Sohn, Seo Yean; Häggblom, Max M
Organohalogen pollutants are of concern in many river and estuarine environments, such as the New York-New Jersey Harbor estuary and its tributaries. The Hackensack River is contaminated with various metals, hydrocarbons and halogenated organics, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins. In order to examine the potential for microbial reductive dechlorination by indigenous microorganisms, sediment samples were collected from five different estuarine locations along the Hackensack River. Hexachlorobenzene (HCB), hexabromobenzene (HBB), and pentachloroaniline (PCA) were selected as model organohalogen pollutants to assess anaerobic dehalogenating potential. Dechlorinating activity of HCB and PCA was observed in sediment microcosms for all sampling sites. HCB was dechlorinated via pentachlorobenzene (PeCB) and trichlorobenzene (TriCB) to dichlorobenzene (DCB). PCA was dechlorinated via tetrachloroaniline (TeCA), trichloroanilines (TriCA), and dichloroanilines (DCA) to monochloroaniline (MCA). No HBB debromination was observed over 12 months of incubation. However, with HCB as a co-substrate slow HBB debromination was observed with production of tetrabromobenzene (TeBB) and tribromobenzene (TriBB). Chloroflexi specific 16S rRNA gene PCR-DGGE followed by sequence analysis detected Dehalococcoides species in sediments of the freshwater location, but not in the estuarine site. Analysis targeting 12 putative reductive dehalogenase (rdh) genes showed that these were enriched concomitant with HCB or PCA dechlorination in freshwater sediment microcosms. Copyright © 2016 Elsevier Ltd. All rights reserved.
Utilization of waste polyethylene terephthalate as a reducing agent in the reduction of iron ore composite pellets
Polat, Gökhan; Birol, Burak; Sarıdede, Muhlis Nezihi
The increasing consumption of plastics inevitably results in increasing amounts of waste plastics. Because of their long degradation periods, these wastes negatively affect the natural environment. Numerous studies have been conducted to recycle and eliminate waste plastics. The potential for recycling waste plastics in the iron and steel industry has been underestimated; the high C and H contents of plastics may make them suitable as alternative reductants in the reduction process of iron ore. This study aims to substitute plastic wastes for coal in reduction melting process and to investigate their performance during reduction at high temperature. We used a common type of waste plastic, polyethylene terephthalate (PET), because of its high carbon and hydrogen contents. Composite pellets containing PET wastes, coke, and magnetite iron ore were reduced at selected temperatures of 1400 and 1450°C for reduction time from 2 to 10 min to investigate the reduction melting behavior of these pellets. The results showed that an increased temperature and reduction time increased the reduction ratio of the pellets. The optimum experimental conditions for obtaining metallic iron (iron nuggets) were reduction at 1450°C for 10 min using composite pellets containing 60% PET and 40% coke.
Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade
El-Sepelgy, Osama; Brzozowska, Aleksandra; Rueping, Magnus
. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high
Temporal fluctuations in grain size, organic materials and iron concentrations in intertidal surface sediment of San Francisco Bay
Thomson-Becker, E. A.; Luoma, S.N.
The physical and chemical characteristics of the oxidized surface sediment in an estuary fluctuate temporally in response to physical forces and apparently-fluctuating inputs. These characteristics, which include grain size and concentrations of organic materials and iron, will influence both trace-metal geochemistry and bioavailability. Temporal trends in the abundance of fine particles, total organic carbon content (TOC), absorbance of extractable organic material (EOM), and concentration of extractable iron in the sediment of San Francisco Bay were assessed using data sets containing approximately monthly samples for periods of two to seven years. Changes in wind velocity and runoff result in monthly changes in the abundance of fine particles in the intertidal zone. Fine-grained particles are most abundant in the late fall/early winter when runoff is elevated and wind velocities are low; particles are coarser in the summer when runoff is low and wind velocities are consistently high. Throughout the bay, TOC is linearly related to fine particle abundance (r = 0.61). Temporal variability occurs in this relationship, as particles are poor in TOC relative to percent of fine particles in the early rainy season. Iron-poor particles also appear to enter the estuary during high runoff periods; while iron is enriched on particle surfaces in the summer. Concentrations of extractable iron and absorbance of EOM vary strongly from year to year. Highest absorbances of EOM occurred in the first year following the drought in 1976-77, and in 1982 and 1983 when river discharge was unusually high. Extractable-iron concentrations were also highest in 1976-77, but were very low in 1982 and 1983. ?? 1985 Dr W. Junk Publishers.
Can sediments at hydrocarbon seep sites represent a source for marine bioavailable iron? — A case study from the South China Sea
Li, N.; Feng, D.; Chen, D.
Niu Li1, Dong Feng1,2, and Duofu Chen2,31CAS Key Laboratory of Ocean and Marginal Sea Geology, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China. 2Laboratory for Marine Geology, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266061, China. 3Hadal Science and Technology Research Center, College of Marine Sciences, Shanghai Ocean University, Shanghai 201306, China. Iron is an essential micronutrient and commonly considered to be one of the key-limiting factors for biological productivity in many ocean regions. Seafloor Fe supply should be most efficient in suboxic conditions. Recent studies shown that widely spread anoxic environments can develop in hydrocarbon seep sediment and local bottom water, owing to the occurrence of aerobic and/or anaerobic methane oxidation. Under this condition, the iron in sediment can be reduced to dissolved Fe2+ in the ocean. However, questions remain about whether the hydrocarbon seep sediment can represent a source for bioavailable iron to the ocean, and the control factor for the transformation of iron in the sediment remains largely unexplored. For a number of hydrocarbon seeps from the northern and southern South China Sea, the iron speciation, pyrite sulfur isotope, and iron isotope, as well as the major and trace elements are used to constrain the intensity of cold seep, and its impact on transformation of iron in sediment. Samples from both areas show sediment iron lost during the high methane flux conditions, owing to the suboxic conditions cause by aerobic methane oxidation. On the other hand, high sediment iron content accompanied by high sulfur content can be seen during the conditions of high methane flux without the occurrence of aerobic methane oxidation, which is possible ascribed to the anaerobic methane oxidation and the release of iron through seep activity. This study reveals the transformation of iron in the sediment is closely related to the
Sediment studies of the biological factors controlling the reduction of U(VI)
International Nuclear Information System (INIS)
Lovley, Derek R.
Studies were conducted primarily with sediments, both in laboratory incubations and in a field experiment, with supporting studies with pure cultures. To our knowledge the sediment studies were the first on microbial U(VI) reduction in actual uranium-contaminated subsurface sediments, under conditions that mimic those found in situ. Important findings included: (1) U(VI) reduction is a biotic process in subsurface sediments. (2) U(VI) reduction can be stimulated most effectively with the addition of acetate. Although it had been speculated that microbial U(VI) reduction might be capable of this type of environmental remediation ever since the discovery of microbial U(VI) reduction, this had not been previously demonstrated under environmentally relevant conditions. (3) U(VI) is reduced concurrently with Fe(III) and prior to sulfate reduction. U(VI) and Fe(III) reduction proceeded concurrently, accompanied by a dramatic enrichment in organisms in the Geobacteraceae. Sulfate-reducing microorganisms do not appear to be important components of the microbial community reducing U(VI) in these subsurface sediments. (4) Nitrate has important influences on U(VI) reduction. Nitrate inhibits the reduction of metals until nitrate is depleted. Fe(III)-reducing microorganisms such as Geobacter metallireducens and Desulfitobacterium species can oxidize Fe(II) with the reduction of nitrate which is an important consideration because our previous studies have demonstrated that freshly precipitated Fe(III) oxides can reoxidize U(IV) to U(VI). The discovery that G. metallireducens can ''run backwards'' and oxidize U(IV) when nitrate is present reveals another mechanism preventing precipitation of U(IV) in the presence of nitrate as well as potential novel strategy for removing uranium from the subsurface after a site has been remediated. (5) Importance of understanding Fe(III) forms available for microbial reduction. Fe(III) is orders of magnitude more abundant than U(VI) as an
Biogeochemistry of Fe and Tc Reduction and Oxidation in FRC Sediment
International Nuclear Information System (INIS)
John M, Zachara; James K, Fredrickson; Ravi K, Kukkadapu; Steven C, Smith; David W, Kennedy
The objectives are: (1) To rigorously characterize the distribution of Fe(II) and Fe(III) in FRC sediment. (2) To identify changes to Fe(II)/Fe(III) distribution and concentration resulting from DIRB activity. (3) To determine the dependence of Tc(VII) reduction rate on biogenic Fe(II) and it's forms. (4) To establish tendency of Tc(IV) and biogenic Fe(II) to oxidize and their effects on Tc immobilization. The mineralogic and chemical properties of the pristine, bioreduced, and chemically extracted FRC sediments were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray microscopy (XRM, at the PNC-CAT beamline at APS), Moessbauer spectroscopy, and scanning and transmission electron microscopy with lattice fringe imaging. Chemical extraction included dithionite-citrate-bicarbonate (DCB), acid ammonium oxalate (AAO), and hydroxylamine hydrochloride (HAH). The FRC sediment was incubated under anoxic conditions with the facultative dissimilatory metal-reducing bacterium Shewanella putrefaciens, strain CN32 in defined aqueous solutions/media with bicarbonate and PIPES buffers for time periods exceeding 75 d. Lactate was used as the electron donor. Aqueous and sorbed Fe(II) (ferrozine assay and 0.5 N HCl extraction) and Mn(II) (ICP-MS and 10 mM CuSO 4 extraction), and pH were monitored to define the reduction progress and extent. The bioreduced materials were characterized using the abovementioned techniques. Bioreduced (pasteurized) sediment or chemically extracted/reduced sediment spiked with Fe(II) was washed with a PIPES buffer/electrolyte solution, and spiked with NaTc(VII)O 4 to yield a concentration of 20 (micro)M. The Tc(VII)-spiked samples were agitated and equilibrated at 25 C and sampled over time to assess the Tc(VII) reduction rate. Selected sediment samples containing 20 (micro)M of reduced Tc [Tc(IV)] were subjected to oxidation by: (1) successive headspace replacements of air, and (2) open system equilibration with air. Removed aqueous
Nitrogen reduction pathways in estuarine sediments: Influences of organic carbon and sulfide
Plummer, Patrick; Tobias, Craig; Cady, David
Potential rates of sediment denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA) were mapped across the entire Niantic River Estuary, CT, USA, at 100-200 m scale resolution consisting of 60 stations. On the estuary scale, denitrification accounted for ~ 90% of the nitrogen reduction, followed by DNRA and anammox. However, the relative importance of these reactions to each other was not evenly distributed through the estuary. A Nitrogen Retention Index (NIRI) was calculated from the rate data (DNRA/(denitrification + anammox)) as a metric to assess the relative amounts of reactive nitrogen being recycled versus retained in the sediments following reduction. The distribution of rates and accompanying sediment geochemical analytes suggested variable controls on specific reactions, and on the NIRI, depending on position in the estuary and that these controls were linked to organic carbon abundance, organic carbon source, and pore water sulfide concentration. The relationship between NIRI and organic carbon abundance was dependent on organic carbon source. Sulfide proved the single best predictor of NIRI, accounting for 44% of its observed variance throughout the whole estuary. We suggest that as a single metric, sulfide may have utility as a proxy for gauging the distribution of denitrification, anammox, and DNRA.
The effect of diluting ruthenium by iron in RuxSey catalyst for oxygen reduction
International Nuclear Information System (INIS)
Delacote, Cyril; Lewera, Adam; Pisarek, Marcin; Kulesza, Pawel J.; Zelenay, Piotr; Alonso-Vante, Nicolas
This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru x Se y . The catalysts were obtained by thermal decomposition of Ru 3 (CO) 12 and Fe(CO) 5 in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.
Study on electrolytic reduction with controlled oxygen flow for iron from molten oxide slag containing FeO
Directory of Open Access Journals (Sweden)
Gao Y.M.
Full Text Available A ZrO2-based solid membrane electrolytic cell with controlled oxygen flow was constructed: graphite rod /[O]Fe+C saturated / ZrO2(MgO/(FeO slag/iron crucible. The feasibility of extraction of iron from molten oxide slag containing FeO at an applied voltage was investigated by means of the electrolytic cell. The effects of some important process factors on the FeO electrolytic reduction with the controlled oxygen flow were discussed. The results show that: solid iron can be extracted from molten oxide slag containing FeO at 1450ºC and an applied potential of 4V. These factors, such as precipitation and growth of solid iron dendrites, change of the cathode active area on the inner wall of the iron crucible and ion diffusion flux in the molten slag may affect the electrochemical reaction rate. The reduction for Fe2+ ions mainly appears on new iron dendrites of the iron crucible cathode, and a very small amount of iron are also formed on the MSZ (2.18% MgO partially stabilized zirconia tube/slag interface due to electronic conductance of MSZ tube. Internal electronic current through MSZ tube may change direction at earlier and later electrolytic reduction stage. It has a role of promoting electrolytic reduction for FeO in the molten slag at the earlier stage, but will lower the current efficiency at the later stage. The final reduction ratio of FeO in the molten slag can achieve 99%. A novel electrolytic method with controlled oxygen flow for iron from the molten oxide slag containing FeO was proposed. The theory of electrolytic reduction with the controlled oxygen flow was developed.
The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries.
Peijnenburg, W; Eriksson, L; de Groot, A; Sjöström, M; Verboom, H
Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.
Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge
Energy Technology Data Exchange (ETDEWEB)
Gonzalez-Silva, Blanca M. [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Briones-Gallardo, Roberto [Facultad de Ingenieria-Instituto de Metalurgia, Universidad Autonoma de San Luis Potosi, Sierra Leona 550, Lomas 2a. Seccion, 78210, San Luis Potosi, S.L.P. (Mexico); Razo-Flores, Elias [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico); Celis, Lourdes B., E-mail: firstname.lastname@example.com [Division de Ciencias Ambientales, Instituto Potosino de Investigacion Cientifica y Tecnologica, Camino a la Presa San Jose 2055, Lomas 4a. Seccion, 78216, San Luis Potosi, S.L.P. (Mexico)
This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe{sup 2+}, 4.0-8.5 mM), cadmium (Cd{sup 2+}, 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO{sub 4}{sup 2-} (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe{sup 2+} (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd{sup 2+} the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.
Inhibition of sulfate reduction by iron, cadmium and sulfide in granular sludge
International Nuclear Information System (INIS)
Gonzalez-Silva, Blanca M.; Briones-Gallardo, Roberto; Razo-Flores, Elias; Celis, Lourdes B.
This study investigated the inhibition effect of iron, cadmium and sulfide on the substrate utilization rate of sulfate reducing granular sludge. A series of batch experiments in a UASB reactor were conducted with different concentrations of iron (Fe 2+ , 4.0-8.5 mM), cadmium (Cd 2+ , 0.53-3.0 mM) and sulfide (4.2-10.6 mM), the reactor was fed with ethanol at 1 g chemical oxygen demand (COD)/L and sulfate to yield a COD/SO 4 2- (g/g) ratio of 0.5. The addition of iron, up to a concentration of 8.1 mM, had a positive effect on the substrate utilization rate which increased 40% compared to the rate obtained without metal addition (0.25 g COD/g VSS-d). Nonetheless, iron concentration of 8.5 mM inhibited the specific substrate utilization rate by 57% compared to the substrate utilization rate obtained in the batch amended with 4.0 mM Fe 2+ (0.44 g COD/g VSS-d). Cadmium had a negative effect on the specific substrate utilization rate at the concentrations tested; at 3.0 mM Cd 2+ the substrate utilization rate was inhibited by 44% compared with the substrate utilization rate without metal addition. Cadmium precipitation with sulfide did not decrease the inhibition of cadmium on sulfate reduction. These results could have important practical implications mainly when considering the application of the sulfate reducing process to treat effluents with high concentrations of sulfate and dissolved metals such as iron and cadmium.
Iron Oxide Minerals in Atmospheric Dust and Source Sediments-Studies of Types and Properties to Assess Environmental Effects
Reynolds, R. L.; Goldstein, H. L.; Moskowitz, B. M.; Till, J. L.; Flagg, C.; Kokaly, R. F.; Munson, S.; Landry, C.; Lawrence, C. R.; Hiza, M. M.; D'Odorico, P.; Painter, T. H.
Ferric oxide minerals in atmospheric dust can influence atmospheric temperatures, accelerate melting of snow and ice, stimulate marine phytoplankton productivity, and impact human health. Such effects vary depending on iron mineral type, size, surface area, and solubility. Generally, the presence of ferric oxides in dust is seen in the red, orange, or yellow hues of plumes that originate in North Africa, central and southwest Asia, South America, western North America, and Australia. Despite their global importance, these minerals in source sediments, atmospheric dust, and downwind aeolian deposits remain poorly described with respect to specific mineralogy, particle size and surface area, or presence in far-traveled aerosol compounds. The types and properties of iron minerals in atmospheric dust can be better understood using techniques of rock magnetism (measurements at 5-300 K), Mössbauer and high-resolution visible and near-infrared reflectance spectroscopy; chemical reactivity of iron oxide phases; and electron microscopy for observing directly the ferric oxide coatings and particles. These studies can elucidate the diverse environmental effects of iron oxides in dust and can help to identify dust-source areas. Dust-source sediments from the North American Great Basin and Colorado Plateau deserts and the Kalahari Desert, southern Africa, were used to compare average reflectance values with a magnetic parameter (hard isothermal remanent magnetization, HIRM) for ferric oxide abundance. Lower reflectance values correspond strongly with higher HIRM values, indicating that ferric oxides (hematite or goethite, or both) contribute to absorption of solar radiation in these sediments. Dust deposited to snow cover of the San Juan Mountains (Colorado) and Wasatch Mountains (Utah) was used to characterize dust composition compared with properties of sediments exposed in source-areas identified from satellite retrievals. Results from multiple methods indicate that
Detoxification of PAX-21 ammunitions wastewater by zero-valent iron for microbial reduction of perchlorate
Energy Technology Data Exchange (ETDEWEB)
Ahn, Se Chang; Cha, Daniel K. [Department of Civil and Environmental Engineering, University of Delaware, Newark, DE 19716 (United States); Kim, Byung J. [U.S. Army Engineer Research and Development Center, Champaign, IL 61826-9005 (United States); Oh, Seok-Young, E-mail: firstname.lastname@example.com [Department of Civil and Environmental Engineering, University of Ulsan, Ulsan 680-749 (Korea, Republic of)
Highlights: {yields} Ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. {yields} DNAN is identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. {yields} Iron treatment not only removes energetic compounds but also eliminates the toxic constituents that inhibit the subsequent microbial process. - Abstract: US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO{sub 4}{sup -}) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21
Characterization of a tricationic trigonal bipyramidal iron(IV) cyanide complex, with a very high reduction potential, and its iron(II) and iron(III) congeners.
England, Jason; Farquhar, Erik R; Guo, Yisong; Cranswick, Matthew A; Ray, Kallol; Münck, Eckard; Que, Lawrence
Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of nonheme oxygen activating enzymes. The trigonal bipyramidal complex [Fe(IV)(O)(TMG(3)tren)](2+) (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG(3)tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [Fe(IV)(CN)(TMG(3)tren)](3+) (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [Fe(II)(CN)(TMG(3)tren)](+) (2), via the S = 5/2 complex [Fe(III)(CN)(TMG(3)tren)](2+) (3), the progress of which was conveniently monitored by using UV-vis spectroscopy to follow the growth of bathochromically shifting ligand-to-metal charge transfer (LMCT) bands. A combination of X-ray absorption spectroscopy (XAS), Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, extended X-ray absorption fine structure (EXAFS) analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an Fe(IV/III) reduction potential of ∼1.4 V vs Fc(+/o), the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t(1/2) in CD(3)CN solution containing 0.1 M KPF(6) at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to (13)C NMR at -40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG(3)tren ligand to support highly charged high-valent complexes.
Optimization and modeling of reduction of wastewater sludge water content and turbidity removal using magnetic iron oxide nanoparticles (MION).
Hwang, Jeong-Ha; Han, Dong-Woo
Economic and rapid reduction of sludge water content in sewage wastewater is difficult and requires special advanced treatment technologies. This study focused on optimizing and modeling decreased sludge water content (Y1) and removing turbidity (Y2) with magnetic iron oxide nanoparticles (Fe3O4, MION) using a central composite design (CCD) and response surface methodology (RSM). CCD and RSM were applied to evaluate and optimize the interactive effects of mixing time (X1) and MION concentration (X2) on chemical flocculent performance. The results show that the optimum conditions were 14.1 min and 22.1 mg L(-1) for response Y1 and 16.8 min and 8.85 mg L(-1) for response Y2, respectively. The two responses were obtained experimentally under this optimal scheme and fit the model predictions well (R(2) = 97.2% for Y1 and R(2) = 96.9% for Y2). A 90.8% decrease in sludge water content and turbidity removal of 29.4% were demonstrated. These results confirm that the statistical models were reliable, and that the magnetic flocculation conditions for decreasing sludge water content and removing turbidity from sewage wastewater were appropriate. The results reveal that MION are efficient for rapid separation and are a suitable alterative to sediment sludge during the wastewater treatment process.
Arsenic enrichment in estuarine sediments-impact of iron and manganese mining
Digital Repository Service at National Institute of Oceanography (India)
Nair, M.; Joseph, T.; Balachandran, K.K.; Nair, K.K.C.; Paimpillii, J.S.
River Mandovi and Zuari, Goa (west coast of India) are flowing through iron and manganese mining areas and are heavily used for iron and manganese ore transport. This region generates 25-30 million tons of mining rejects per year. The iron ore...
Bacterial Oxidation and Reduction of Iron in the Processes of Creation and Treatment of Acid Mining Waters
Directory of Open Access Journals (Sweden)
Daniel Kupka
Full Text Available 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 living in these environments are acidophilic ferric iron reducing bacteria. This group of microorganisms has been discovered only relatively recently. Acidophilic heterotrophic bacteria reduce ferric iron in either soluble or solid forms to ferrous iron. The reductive dissolution of ferric iron minerals brings about a mobilization of iron as well as associated heavy metals. The Bacterial oxidation and reduction of iron play an important role in the transformation of either crystalline or amorphous iron-containing minerals, including sulphides, oxides, hydroxysulfates, carbonates and silicates. This work discusses the role of acidophilic bacteria in the natural iron cycling and the genesis of acidic effluents. The possibilities of application of iron bacteria in the remediation of AMDs are also considered.
Uranium(VI) Reduction by Nanoscale Zerovalent Iron in Anoxic Batch Systems
International Nuclear Information System (INIS)
Yan, Sen; Hua, Bin; Bao, Zhengyu; Yang, John; Liu, Chongxuan; Deng, Baolin
This study investigated the influences of pH, bicarbonate, and calcium on U(VI) adsorption and reduction by synthetic nanosize zero valent iron (nano Fe 0 ) particles under an anoxic condition. The results showed that about 87.1%, 82.7% and 78.3% of U(VI) could be reduced within 96 hours in the presence of 10 mM bicarbonate at pHs 6.92, 8.03 and 9.03, respectively. The rates of U(VI) reduction and adsorption by nano Fe 0 , however, varied significantly with increasing pH and concentrations of bicarbonate and/or calcium. Solid phase analysis by X-ray photoelectron spectroscopy confirmed the formation of UO 2 and iron (hydr)oxides as a result of the redox interactions between adsorbed U(VI) and nano Fe 0 . This study highlights the potential important role of groundwater chemical composition in controlling the rates of U(VI) reductive immobilization using nano Fe 0 in subsurface environments.
Copper increases reductive dehalogenation of haloacetamides by zero-valent iron in drinking water: Reduction efficiency and integrated toxicity risk.
Chu, Wenhai; Li, Xin; Bond, Tom; Gao, Naiyun; Bin, Xu; Wang, Qiongfang; Ding, Shunke
The haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs), are highly cytotoxic and genotoxic, and typically occur in treated drinking waters at low μg/L concentrations. Since many drinking distribution and storage systems contain unlined cast iron and copper pipes, reactions of HAcAms with zero-valent iron (ZVI) and metallic copper (Cu) may play a role in determining their fate. Moreover, ZVI and/or Cu are potentially effective HAcAm treatment technologies in drinking water supply and storage systems. This study reports that ZVI alone reduces trichloroacetamide (TCAcAm) to sequentially form dichloroacetamide (DCAcAm) and then monochloroacetamide (MCAcAm), whereas Cu alone does not impact HAcAm concentrations. The addition of Cu to ZVI significantly improved the removal of HAcAms, relative to ZVI alone. TCAcAm and their reduction products (DCAcAm and MCAcAm) were all decreased to below detection limits at a molar ratio of ZVI/Cu of 1:1 after 24 h reaction (ZVI/TCAcAm = 0.18 M/5.30 μM). TCAcAm reduction increased with the decreasing pH from 8.0 to 5.0, but values from an integrated toxic risk assessment were minimised at pH 7.0, due to limited removal MCAcAm under weak acid conditions (pH = 5.0 and 6.0). Higher temperatures (40 °C) promoted the reductive dehalogenation of HAcAms. Bromine was preferentially removed over chlorine, thus brominated HAcAms were more easily reduced than chlorinated HAcAms by ZVI/Cu. Although tribromoacetamide was more easily reduced than TCAcAm during ZVI/Cu reduction, treatment of tribromoacetamide resulted in a higher integrated toxicity risk than TCAcAm, due to the formation of monobromoacetamide (MBAcAm). Copyright © 2016 Elsevier Ltd. All rights reserved.
Kinetics and Products of Chromium(VI) Reduction by Iron(II/III)-Bearing Clay Minerals.
Joe-Wong, Claresta; Brown, Gordon E; Maher, Kate
Hexavalent chromium is a water-soluble pollutant, the mobility of which can be controlled by reduction of Cr(VI) to less soluble, environmentally benign Cr(III). Iron(II/III)-bearing clay minerals are widespread potential reductants of Cr(VI), but the kinetics and pathways of Cr(VI) reduction by such clay minerals are poorly understood. We reacted aqueous Cr(VI) with two abiotically reduced clay minerals: an Fe-poor montmorillonite and an Fe-rich nontronite. The effects of ionic strength, pH, total Fe content, and the fraction of reduced structural Fe(II) [Fe(II)/Fe(total)] were examined. The last variable had the largest effect on Cr(VI) reduction kinetics: for both clay minerals, the rate constant of Cr(VI) reduction varies by more than 3 orders of magnitude with Fe(II)/Fe(total) and is described by a linear free energy relationship. Under all conditions examined, Cr and Fe K-edge X-ray absorption near-edge structure spectra show that the main Cr-bearing product is a Cr(III)-hydroxide and that Fe remains in the clay structure after reacting with Cr(VI). This study helps to quantify our understanding of the kinetics of Cr(VI) reduction by Fe(II/III)-bearing clay minerals and may improve predictions of Cr(VI) behavior in subsurface environments.
Magnetic and Moessbauer-spectroscopic studies of iron-clusters in zeolites. [Reduction of ferrous ions
Energy Technology Data Exchange (ETDEWEB)
Schmidt, F; Gunsser, W; Knappwost, A [Hamburg Univ. (F.R. Germany). Inst. fuer Physikalische Chemie
Iron clusters have been prepared within zeolite holes by reduction of zeolites containing ferrous ions. The diameter of these particles must therefore be smaller that 13 A. They are superparamagnetic and their Moessbauer spectra show no HFS, even at 4K. The temperature dependence of the magnetic susceptibility of the unreduced zeolites obeys a Curie-Weiss law with p/sub eff/ = 4.45 ..mu..B and THETA = 105K. The Weiss curves of the reduced samples lie distinctly below those of the bulk material.
Optimization of colorimetric DET technique for the in situ, two-dimensional measurement of iron(II) distributions in sediment porewaters
DEFF Research Database (Denmark)
Bennett, William W.; Teasdale, Peter R.; Welsh, David T.
The recently developed colorimetric diffusive equilibration in thin films (DET) technique for the in situ, high-resolution measurement of iron(II) in marine sediments is optimized to allow measurement of the higher iron concentrations typical of freshwater sediment porewaters. Computer imaging...... the sensitivity of the assay as required; by processing the image with different color channel filters, the sensitivity of the assay can be optimized for lower concentrations (up to 100 μmol L -1) or higher concentrations (up to 2000 μmol L -1) of iron(II), depending on the specific site characteristics......(II) in sediment porewaters. The detection limit of the optimized technique was 4.1 ± 0.3 μmol L -1 iron(II) and relative standard deviations were less than 6%....
Microbial Sulfate Reduction in Deep-Sea Sediments at the Guaymas Basin - Hydrothermal Vent Area - Influence of Temperature and Substrates
DEFF Research Database (Denmark)
Microbial sulfate reduction was studied by a S-35 tracer technique in sediments from the hydrothermal vent site in Guaymas Basin, Gulf of California, Mexico. In situ temperatures ranged from 2.7-degrees-C in the overlying seawater to > 120-degrees-C at 30 cm depth in the hydrothermal sediment...
Offshore sediments record the history of onshore iron ore mining in Goa State, India
Digital Repository Service at National Institute of Oceanography (India)
Sebastian, T.; Nath, B.N.; Naik, Sangeeta; Borole, D.V.; Pierre, S.; Yazing, A.K.
Environmental magnetic and geochemical analyses combined with 210Pb dating were carried out on a sediment core off Goa from Arabian Sea to reconstruct the sedimentation history of last three and a half centuries and to investigate the impact...
Operational experience on reduction of feedwater iron and liquid radwaste input for Kuosheng Nuclear Power Plant
International Nuclear Information System (INIS)
Wen, T.J.; Huang, Theresa Chen; Liu, Wen Tsung; Liu, T.C.; Shyur, Tzu Sheng; Shen, S.C.
Other than cobalt alloys, or low cobalt materials, feedwater iron content plays an important role in crud activation and transport causing the growth of out-of-core radiation fields and associated with radwaste generation. Before installing prefilter in the upstream of condensate deep-bed demineralizer, increasing demand for suspended solid removal required new backwash and regeneration technique in Kuosheng Nuclear Power Plant. At steady state full power operation, the average iron concentration in condensate demineralizer influent was 8-15 ppb. Considering both the necessity of backwash and reduction of liquid radwaste input, several actions had been taken to promote the crud removal capabilities without using ultrasonic resin cleaner and controlled feedwater iron content between 0.5 and 2.0 ppb. This modified resin backwash technique would also generate minimum liquid radwaste. Meanwhile, significant efforts have been made to promote the quality of waste water by carefully control input streams as well as backwash modification to reduce liquid radwaste generation. The daily quantity of liquid radwaste has decreased dramatically in the past two years and is effectively controlled under the expected average daily input of design basis. (author)
Measurement of aerosol size distribution by impaction and sedimentation An experimental study and data reduction
International Nuclear Information System (INIS)
Diouri, Mohamed.
This study concerns essentially solid aerosols produced by combustion and more particulary the aerosol liberated by a sodium fire taken into account in safety studies related to sodium cooled nuclear reactors. The accurate determination of the aerosol size distribution depends on the selection device use. An experimental study of the parameters affecting the solid aerosol collection efficiency was made with the Andersen Mark II cascade impactor (blow off and bounce, electrical charge of particles, wall-loss). A sedimentation chamber was built and calibrated for the range between 4 and 10 μm. The second part describes a comparative study of different data reduction methods for the impactor and a new method for setting up the aerosol size distribution with data obtained by the sedimentation chamber [fr
Fine sediment transport into the hyperturbid lower Ems River : The role of channel deepening and sediment-induced drag reduction
Van Maren, D.S.; Winterwerp, J.C.; Vroom, J.
Deepening of estuarine tidal channels often leads to tidal amplification and increasing fine sediment import. Increasing fine sediment import, in turn, may lower the hydraulic drag (due to a smoother muddy bed and/or sediment-induced damping of turbulence), and therefore, further strengthen tidal
Application of nonisothermal kinetic techniques on the reduction of three commercial iron ore agglomerates
International Nuclear Information System (INIS)
Bedolla, E.; Leon, C.A.; Aguilar, E.A.
The mechanism of reduction of iron ore agglomerates by both isothermal and nonisothermal TG studies was investigated, and the work was complemented with the structural characterization of the total and partially reacted samples. Three different commercial hematite pellets were studied. The mechanisms of reduction were obtained under isothermal conditions, resulting in a fitting to chemical reaction models. Nonisothermal reduction was carried out using a TGA system (CAHN TG-171) from 600 to 1,000 degree centigree maintaining a lineal heating rate of 4,7 and 10 degree centigree/min, and the reducing atmospheres used were H 2 (100%) and H 2 -CO(95:5). The kinetic parameters were evaluated by Coats and Redfern, Dixit and Ray and Prakash and Ray techniques. It was found that the lower the heating rate, the higher the reduction degree and the higher activation energy. The activation energy for reduction with the mixture H 2 -CO was always higher than that obtained with pure H 2 . (Author)
Electrochemical preparation of iron cuboid nanoparticles and their catalytic properties for nitrite reduction
International Nuclear Information System (INIS)
Chen Yanxin; Chen Shengpei; Chen Qingsong; Zhou Zhiyou; Sun Shigang
Iron cuboid nanoparticles supported on glassy carbon (denoted nm-Fe/GC) were prepared by electrochemical deposition under cyclic voltammetric (CV) conditions. The structure and composition of the Fe nanomaterials were characterized by scanning electron microscopy (SEM), selected area electron diffraction (SAED), X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX). The results demonstrated that the Fe cuboid nanoparticles are dispersed discretely on GC substrate with an average size ca. 171 nm, and confirmed that the electrochemical synthesized nanocubes are single crystals of pure Fe. The catalytic properties of the Fe cuboid nanoparticles towards nitrite electroreduction were investigated, and enhanced electrocatalytic activity of the Fe nanocubes has been determined. In comparison with the data obtained on a bulk-Fe electrode, the onset potential of nitrite reduction on nm-Fe/GC is positively sifted by 100 mV, and the steady reduction current density is enhanced about 2.4-3.2 times
Carbothermic Reduction of Nickeliferous Laterite Ores for Nickel Pig Iron Production in China: A Review
Rao, Mingjun; Li, Guanghui; Jiang, Tao; Luo, Jun; Zhang, Yuanbo; Fan, Xiaohui
Both the consumption and production of crude stainless steel in China rank first in the world. In 2011, the nickel production in China amounted to 446 kilotons, with the proportion of electrolytic nickel and nickel pig iron (NPI) registering 41.5% and 56.5%, respectively. NPI is a low-cost feedstock for stainless steel production when used as a substitute for electrolytic nickel. The existing commercial NPI production processes such as blast furnace smelting, rotary kiln-electric furnace smelting, and Krupp-Renn (Nipon Yakin Oheyama) processes are discussed. As low-temperature (below 1300°C) reduction of nickeliferous laterite ores followed by magnetic separation could provide an alternative avenue without smelting at high temperature (~1500°C) for producing ferronickel with low cost, the fundamentals and recent developments of the low-temperature reduction of nickeliferous laterite ores are reviewed.
Biotic and a-biotic Mn and Fe cycling in deep sediments across a gradient of sulfate reduction rates along the California margin
Schneider-Mor, A.; Steefel, C.; Maher, K.
The coupling between the biological and a-biotic processes controlling trace metals in deep marine sediments are not well understood, although the fluxes of elements and trace metals across the sediment-water interface can be a major contribution to ocean water. Four marine sediment profiles (ODP leg 167 sites 1011, 1017, 1018 and 1020)were examined to evaluate and quantify the biotic and abiotic reaction networks and fluxes that occur in deep marine sediments. We compared biogeochemical processes across a gradient of sulfate reduction (SR) rates with the objective of studying the processes that control these rates and how they affect major elements as well as trace metal redistribution. The rates of sulfate reduction, methanogenesis and anaerobic methane oxidation (AMO) were constrained using a multicomponent reactive transport model (CrunchFlow). Constraints for the model include: sediment and pore water concentrations, as well as %CaCO3, %biogenic silica, wt% carbon and δ13C of total organic carbon (TOC), particulate organic matter (POC) and mineral associated carbon (MAC). The sites are distinguished by the depth of AMO: a shallow zone is observed at sites 1018 (9 to 19 meters composite depth (mcd)) and 1017 (19 to 30 mcd), while deeper zones occur at sites 1011 (56 to 76 mcd) and 1020 (101 to 116 mcd). Sulfate reduction rates at the shallow AMO sites are on the order 1x10-16 mol/L/yr, much faster than rates in the deeper zone sulfate reduction (1-3x10-17 mol/L/yr), as expected. The dissolved metal ion concentrations varied between the sites, with Fe (0.01-7 μM) and Mn (0.01-57 μM) concentrations highest at Site 1020 and lowest at site 1017. The highest Fe and Mn concentrations occurred at various depths, and were not directly correlated with the rates of sulfate reduction and the maximum alkalinity values. The main processes that control cycling of Fe are the production of sulfide from sulfate reduction and the distribution of Fe-oxides. The Mn distribution
Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination
Moulin, Solenne
Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knölker\\'s complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knölker\\'s complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron-dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Festival of amination: Two series of modified Knölker\\'s complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Impact of natural organic matter coatings on the microbial reduction of iron oxides
Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg
Iron (Fe) oxyhydroxides are important constituents of the soil mineral phase known to stabilize organic matter (OM) under oxic conditions. In an anoxic milieu, however, these Fe-organic associations are exposed to microbial reduction, releasing OM into soil solution. At present, only few studies have addressed the influence of adsorbed natural OM (NOM) on the reductive dissolution of Fe oxyhydroxides. This study therefore examined the impact of both the composition and concentration of adsorbed NOM on microbial Fe reduction with regard to (i) electron shuttling, (ii) complexation of Fe(II,III), (iii) surface site coverage and/or pore blockage, and (iv) aggregation. Adsorption complexes with varying carbon loadings were synthesized using different Fe oxyhydroxides (ferrihydrite, lepidocrocite, goethite, hematite, magnetite) and NOM of different origin (extracellular polymeric substances from Bacillus subtilis, OM extracted from soil Oi and Oa horizons). The adsorption complexes were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), N2 gas adsorption, electrophoretic mobility and particle size measurements, and OM desorption. Incubation experiments under anaerobic conditions were conducted for 16 days comparing two different strains of dissimilatory Fe(III)-reducing bacteria (Shewanella putrefaciens, Geobacter metallireducens). Mineral transformation during reduction was assessed via XRD and FTIR. Microbial reduction of the pure Fe oxyhydroxides was controlled by the specific surface area (SSA) and solubility of the minerals. For Shewanella putrefaciens, the Fe reduction of adsorption complexes strongly correlated with the concentration of potentially usable electron-shuttling molecules for NOM concentrations <2 mg C L-1, whereas for Geobacter metallireducens, Fe reduction depended on the particle size and thus aggregation of the adsorption complexes. These diverging results suggest that
Sedimentation separation and fluorescent X-ray analysis of very small amount of cobalt in pure iron
International Nuclear Information System (INIS)
Kato, Kensaku
As the simple method of separation and analysis of very small amount of cobalt up to 1 ppm in pure iron, the application of sedimentation separation and fluorescent X-ray analysis was examined. By adding citric acid to the sample solution, the masking of the main components was carried out, and cobalt was deposited with 2-nitroso 1-naphtol separated and concentrated on a membrane filter. The reagents and equipments used are shown. The operation of the fundamental quantitative determination was determined. The condition of measurement, the condition of sedimentation separation, the effect of coexisting elements, the rate of recovery of cobalt, the calibration curve, and the analysis of actual samples are reported. By separating and concentrating cobalt on a membrane filter, this method eliminates the obstruction of coexisting elements to the object element, which is the problem in fluorescent X-ray measurement, and has the merit of simple operation and wide range of quantitative determination. (K.I.)
Understanding the role of multiheme cytochromes in iron(III) reduction and arsenic mobilization by Shewanella sp. ANA-3
Reyes, C.; Duenas, R.; Saltikov, C.
The reduction of Fe (III) to Fe (II) and of arsenate (As (V)) to arsenite (As (III)) by Fe (III) reducing and As (V) respiring prokaryotes such as the bacterium Shewanella sp. ANA-3 may contribute to arsenic mobilization in aquifers contaminated with arsenic, specifically in places such as Bangladesh. Under oxic conditions As (V) predominates and is often adsorbed onto mineral surfaces such as amorphous ferrihydrite. However, under anoxic conditions As (III) predominates, sorbs to fewer minerals, and has a greater hydrologic mobility compared to As (V). The genetic mechanism underlying arsenic release from subsurface material most likely involves a combination of respiratory gene clusters (e.g. mtr/omc and arr). In this study, we are investigating the genetic pathways underlying arsenic mobilization. We have generated various mutations in the mtr/omc gene cluster, which encodes several outermembrane decaheme c-type cytochromes. Deletions in one mtr/omc gene did not eliminate iron reduction. However, strains carrying multiple gene deletions were greatly impaired in iron reduction abilities. Work is currently underway to generate combinations of iron reduction and arsenate reduction single and double mutants that will be used to investigate microbial mobilization of arsenic in flow-through columns containing As (V)-HFO coated sand. This work will address the importance of arsenate reduction and iron reduction in the mobilization of arsenic.
Methane Migration and Its Influence on Sulfate Reduction in the Good Weather Ridge Region, South China Sea Continental Margin Sediments
Directory of Open Access Journals (Sweden)
Saulwood Lin
Full Text Available Bacteria sulfate reduction is a major pathway for organic carbon oxidation in marine sediments. Upward diffusion of methane from gas hydrate deep in the sedimentary strata might be another important source of carbon for sulfate reducing bacteria and subsequently induce higher rates of sulfate reduction in sediments. Since abundant gas may migrate upward to the surface as a result of tectonic activity occurring in the accretionary wedge, this study investigates the effect of methane migration on the sulfate reduction process in continental margin sediments offshore southwestern Taiwan. Piston and gravity core samples were taken in order to evaluate vertical and spatial variations of sulfate and methane. Pore water sulfate, sulfide, methane, sediment pyrite, and organic carbon were extracted and analyzed.
Asymmetric Chemoenzymatic Reductive Acylation of Ketones by a Combined Iron-Catalyzed Hydrogenation-Racemization and Enzymatic Resolution Cascade
El-Sepelgy, Osama
A general and practical process for the conversion of prochiral ketones into the corresponding chiral acetates has been realized. An iron carbonyl complex is reported to catalyze the hydrogenation-dehydrogenation-hydrogenation of prochiral ketones. By merging the iron-catalyzed redox reactions with enantioselective enzymatic acylations a wide range of benzylic, aliphatic and (hetero)aromatic ketones, as well as diketones, were reductively acylated. The corresponding products were isolated with high yields and enantioselectivities. The use of an iron catalyst together with molecular hydrogen as the hydrogen donor and readily available ethyl acetate as acyl donor make this cascade process highly interesting in terms of both economic value and environmental credentials.
Early diagenesis of manganese, iron and phosphorus in European continental margin sediments
Zee, C. van der
This thesis describes the results of a project that was carried out as a part of the Sedimentary Manganese and Iron cycLEs (SMILE) research program funded by the Netherlands Organisation of Scientific Research (NWO/ALW). SMILE aimed at studying the biogeochemistry of iron and manganese cycles in
Early diagenesis of Manganese, Iron and Phosphorus in European continental margin sediments
van der Zee, C.
This thesis describes the results of a project that was carried out as a part of the Sedimentary Manganese and Iron cycLEs (SMILE) research program funded by the Netherlands Organisation of Scientific Research (NWO/ALW). SMILE aimed at studying the biogeochemistry of iron and manganese cycles in
DEFF Research Database (Denmark)
Hansen, Jakob Bondo; Moen, I W; Mandrup-Poulsen, T
and discuss recent evidence, suggesting that iron is a key pathogenic factor in both type 1 and type 2 diabetes with a focus on inflammatory pathways. Pro-inflammatory cytokine-induced β-cell death is not fully understood, but may include iron-induced ROS formation resulting in dedifferentiation by activation...... of transcription factors, activation of the mitochondrial apoptotic machinery or of other cell death mechanisms. The pro-inflammatory cytokine IL-1β facilitates divalent metal transporter 1 (DMT1)-induced β-cell iron uptake and consequently ROS formation and apoptosis, and we propose that this mechanism provides...
Thermophilic nitrate-reducing microorganisms prevent sulfate reduction in cold marine sediments incubated at high temperature
Nepomnyashchaya, Yana; Rezende, Julia; Hubert, Casey
Hydrogen sulphide produced during metabolism of sulphate-reducing microorganisms (SRM) is toxic, corrosive and causes detrimental oil reservoir souring. During secondary oil recovery, injecting oil reservoirs with seawater that is rich in sulphate and that also cools high temperature formations provides favourable growth conditions for SRM. Nitrate addition can prevent metabolism of SRM by stimulating nitrate-reducing microorganisms (NRM). The investigations of thermophilic NRM are needed to develop mechanisms to control the metabolism of SRM in high temperature oil field ecosystems. We therefore established a model system consisting of enrichment cultures of cold surface marine sediments from the Baltic Sea (Aarhus Bay) that were incubated at 60°C. Enrichments contained 25 mM nitrate and 40 mM sulphate as potential electron acceptors, and a mixture of the organic substrates acetate, lactate, propionate, butyrate (5 mM each) and yeast extract (0.01%) as potential carbon sources and electron donors. Slurries were incubated at 60°C both with and without initial pasteurization at 80°C for 2 hours. In the enrichments containing both nitrate and sulphate, the concentration of nitrate decreased indicating metabolic activity of NRM. After a four-hour lag phase the rate of nitrate reduction increased and the concentration of nitrate dropped to zero after 10 hours of incubation. The concentration of nitrite increased as the reduction of nitrate progressed and reached 16.3 mM after 12 hours, before being consumed and falling to 4.4 mM after 19-day of incubation. No evidence for sulphate reduction was observed in these cultures during the 19-day incubation period. In contrast, the concentration of sulphate decreased up to 50% after one week incubation in controls containing only sulphate but no nitrate. Similar sulfate reduction rates were seen in the pasteurized controls suggesting the presence of heat resistant SRM, whereas nitrate reduction rates were lower in the
Effects of activated carbon on reductive dechlorination of PCBs by organohalide respiring bacteria indigenous to sediments.
Kjellerup, B V; Naff, C; Edwards, S J; Ghosh, U; Baker, J E; Sowers, K R
Polychlorinated biphenyls (PCBs) have accumulated in aquatic sediments due to their inherent chemical stability and their presence poses a risk due to their potential toxicity in humans and animals. Granular activated carbon (GAC) has been applied to PCB contaminated sediment sites to reduce the aqueous concentration by sequestration thus reducing the PCB exposure and toxicity to both benthic and aquatic organisms. However, it is not known how the reduction of PCB bioavailability by adsorption to GAC affects bacterial transformation of PCBs by indigenous organohalide respiring bacteria. In this study, the impact of GAC on anaerobic dechlorination by putative organohalide respiring bacteria indigenous to sediment from Baltimore Harbor was examined. It was shown that the average Cl/biphenyl after dehalogenation of Aroclor 1260 was similar between treatments with and without GAC amendment. However, GAC caused a substantial shift in the congener distribution whereby a smaller fraction of highly chlorinated congeners was more extensively dechlorinated to mono- through tri-chlorinated congeners compared to the formation of tri- through penta-chlorinated congeners in unamended sediment. The results combined with comparative sequence analysis of 16S rRNA gene sequences suggest that GAC caused a community shift to putative organohalide respiring phylotypes that coincided with more extensive dechlorination of ortho and unflanked chlorines. This shift in activity by GAC shown here for the first time has the potential to promote greater degradation in situ by promoting accumulation of less chlorinated congeners that are generally more susceptible to complete mineralization by aerobic PCB degrading bacteria. Copyright © 2013 Elsevier Ltd. All rights reserved.
... Share: Search the ODS website Submit Search NIH Office of Dietary Supplements Consumer Datos en español Health ... eating a variety of foods, including the following: Lean meat, seafood, and poultry. Iron-fortified breakfast cereals ...
Final report - Microbial pathways for the reduction of mercury in saturated subsurface sediments
Energy Technology Data Exchange (ETDEWEB)
Tamar barkay; Lily Young; Gerben Zylstra
Mercury is a component of mixed wastes that have contaminated vast areas of the deep subsurface as a result of nuclear weapon and energy production. While this mercury is mostly bound to soil constituents episodes of groundwater contamination are known in some cases resulting in potable water super saturated with Hg(0). Microbial processes that reduce Hg(II) to the elemental form Hg(0) in the saturated subsurface sediments may contribute to this problem. When we started the project, only one microbial pathway for the reduction of Hg(II), the one mediated by the mer operon in mercury resistant bacteria was known. As we had previously demonstrated that the mer mediated process occurred in highly contaminated environments (Schaefer et al., 2004), and mercury concentrations in the subsurface were reported to be low (Krabbenhoft and Babiarz, 1992), we hypothesized that other microbial processes might be active in reducing Hg(II) to Hg(0) in saturated subsurface environments. The specific goals of our projects were: (1) Investigating the potential for Hg(II) reduction under varying electron accepting conditions in subsurface sediments and relating these potential to mer gene distribution; and (2) Examining the physiological and biochemical characteristics of the interactions of anaerobic bacteria with mercury. The results are briefly summarized with references to published papers and manuscripts in preparation where details about our research can be found. Additional information may be found in copies of our published manuscripts and conference proceedings, and our yearly reports that were submitted through the RIMS system.
Cable bacteria control iron-phosphorus dynamics in sediments of a coastal hypoxic basin
Sulu-Gambari, Fatimah; Seitaj, Dorina; Meysman, Filip J.R.; Schauer, Regina; Polerecky, Lubos; Slomp, Caroline P.
Phosphorus is an essential nutrient for life. The release of phosphorus from sediments is critical in sustaining phytoplankton growth in many aquatic systems and is pivotal to eutrophication and the development of bottom water hypoxia. Conventionally, sediment phosphorus release is thought to be
Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.
Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng
It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.
Arsenic and trace metals in river water and sediments from the southeast portion of the Iron Quadrangle, Brazil.
Varejão, Eduardo V V; Bellato, Carlos R; Fontes, Maurício P F; Mello, Jaime W V
The Iron Quadrangle has been one of the most important gold production regions in Brazil since the end of the seventeenth century. There, arsenic occurs in close association with sulfide-rich auriferous rocks. The most abundant sulfide minerals are pyrite and arsenopyrite, yet trace metal sulfides occur in subordinate phases as well. Historical mining activities have been responsible for the release of As and trace metals to both aquatic and terrestrial environments close to mining sites in the region. Therefore, this study was aimed to evaluate the distribution and mobility of As, Cd, Co, Cr, Cu, Ni, Pb, and Zn in streams in the southeast portion of the Iron Quadrangle between the municipalities of Ouro Preto and Mariana, the oldest Brazilian Au mining province. Total concentrations of some trace metals and arsenic in water were determined. The four-stage sequential extraction procedure proposed by the commission of the European Communities Bureau of Reference (BCR) was used to investigate the distribution of these elements in stream sediments. Arsenic concentration in water was > 10 μg L⁻¹ (maximum limit permitted by Brazilian environmental regulations for water destined for human consumption) at all sampling sites, varying between 36.7 and 68.3 μg L⁻¹. Sequential extraction in sediments showed high concentrations of As and trace metals associated with easily mobilized fractions.
Speciation and spatial distribution of solid-phase iron in surface sediments of the East China Sea continental shelf
International Nuclear Information System (INIS)
Zhu, Mao-Xu; Hao, Xiao-Chen; Shi, Xiao-Ning; Yang, Gui-Peng; Li, Tie
Speciation and reactivity characterization of solid-phase Fe in marine sediments are of significance to understanding its heterogeneous mineralogy and crystallinity, the diagenetic cycling of Fe and its regulating roles on many other elements in sediments. In this study, a combination of sequential and single-step extractions was used for the determination of seven Fe pools in surface sediments of the East China Sea (ECS) continental shelf: (1) carbonate associated Fe (Fe(II) carb ) plus acid volatile sulfide-Fe (Fe(II) AVS ), (2) easily reducible amorphous/poorly crystalline Fe oxides (Fe ox1 ), (3) reducible crystalline Fe oxides (Fe ox2 ), (4) magnetite (Fe mag ), (5) poorly reactive sheet silicate Fe (Fe PRS ), (6) pyrite-Fe (Fe py ), and (7) unreactive silicate Fe (Fe U ). Total Fe (Fe T ) in the sediments is largely determined by terrestrial aluminosilicate particles as indicated by a great similarity of the Fe T with that of the Yangtze River and global riverine particulates. The size of Fe PRS is found to be the largest pool, followed by Fe U , Fe ox2 , Fe mag , Fe(II) AVS+carb , Fe ox1 and Fe py . The large Fe PRS may result from neoformation of Fe-rich clay minerals via reverse weathering and subsequent ageing. The small sizes of Fe(II) AVS+carb and Fe py pools is believed to be the result of low SO 4 reduction due to generally low labile organic matter together with the oxic/suboxic, dynamic environments of the surface sediments. The occurrence of Fe ox1 , Fe ox2 and Fe PRS in the sediments is closely associated with the clay fraction as indicated by a high spatial correlation between the former and the latter. Highly reactive Fe(Fe HR ) in the sediments is comparable to that in global marine sediments, but apparently lower than in the Yangtze River and global riverine particulates due probably to sequestration in the Yangtze Estuary. The ratios of Fe HR /Fe T , Fe PR /Fe T and Fe U /Fe T in the ECS surface sediments consistently show more similarity to
Oxidation of a Dimethoxyhydroquinone by Ferrihydrite and Goethite Nanoparticles: Iron Reduction versus Surface Catalysis.
Krumina, Lelde; Lyngsie, Gry; Tunlid, Anders; Persson, Per
Hydroquinones are important mediators of electron transfer reactions in soils with a capability to reduce Fe(III) minerals and molecular oxygen, and thereby generating Fenton chemistry reagents. This study focused on 2,6-dimethoxy hydroquinone (2,6-DMHQ), an analogue to a common fungal metabolite, and its reaction with ferrihydrite and goethite under variable pH and oxygen concentrations. Combined wet-chemical and spectroscopic analyses showed that both minerals effectively oxidized 2,6-DMHQ in the presence of oxygen. Under anaerobic conditions the first-order oxidation rate constants decreased by one to several orders of magnitude depending on pH and mineral. Comparison between aerobic and anaerobic results showed that ferrihydrite promoted 2,6-DMHQ oxidation both via reductive dissolution and heterogeneous catalysis while goethite mainly caused catalytic oxidation. These results were in agreement with changes in the reduction potential (E H ) of the Fe(III) oxide/Fe(II) aq redox couple as a function of dissolved Fe(II) where E H of goethite was lower than ferrihydrite at any given Fe(II) concentration, which makes ferrihydrite more prone to reductive dissolution by the 2,6-DMBQ/2,6-DMHQ redox couple. This study showed that reactions between hydroquinones and iron oxides could produce favorable conditions for formation of reactive oxygen species, which are required for nonenzymatic Fenton-based decomposition of soil organic matter.
Reduction and Immobilization of Potassium Permanganate on Iron Oxide Catalyst by Fluidized-Bed Crystallization Technology
Directory of Open Access Journals (Sweden)
Guang-Xia Li
Full Text Available A manganese immobilization technology in a fluidized-bed reactor (FBR was developed by using a waste iron oxide (i.e., BT-3 as catalyst which is a by-product from the fluidized-bed Fenton reaction (FBR-Fenton. It was found that BT-3 could easily reduce potassium permanganate (KMnO4 to MnO2. Furthermore, MnO2 could accumulate on the surface of BT-3 catalyst to form a new Fe-Mn oxide. Laboratory experiments were carried out to investigate the KMnO4-reduction mechanism, including the effect of KMnO4 concentration, BT-3 dosage, and operational solution pH. The results showed that the pH solution was a significant factor in the reduction of KMnO4. At the optimum level, pHf 6, KMnO4 was virtually reduced in 10 min. A pseudo-first order reaction was employed to describe the reduction rate of KMnO4.
Role of a gas phase in the kinetics of zinc and iron reduction with carbon from slag melts
Chumarev, V. M.; Selivanov, E. N.
The influence of the mass transfer conditions in the gas phase having formed at the carbon-slag melt interface on CO regeneration is approximately estimated in the framework of a two-stage scheme of metal reduction from slag melts by carbon. The effect of zinc vapors on the combined reduction of iron and zinc from slags is considered. The influence of the slag composition and temperature on the critical concentration of zinc oxide above which no iron forms as an individual phase is explained.
Properties and effects of remaining carbon from waste plastics gasifying on iron scale reduction.
Zhang, Chongmin; Chen, Shuwen; Miao, Xincheng; Yuan, Hao
The carbonous activities of three kinds of carbon-bearing materials gasified from plastics were tested with coal coke as reference. The results showed that the carbonous activities of these remaining carbon-bearing materials were higher than that of coal-coke. Besides, the fractal analyses showed that the porosities of remaining carbon-bearing materials were higher than that of coal-coke. It revealed that these kinds of remaining carbon-bearing materials are conducive to improve the kinetics conditions of gas-solid phase reaction in iron scale reduction. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
Nitrogen fixation (Acetylene reduction) in the sediments of the pluss-see : with special attention to the role of sedimentation
Blauw, T.S.
Sediments of productive lakes are usually rich in organic matter and, except for a thin surficial layer, anaerobic. These conditions seem to be favourable for heterotrophic nitrogen fixation. However, these sediments also contain relatively high ammonium concentrations. Ammonium represses
Microbial Reduction of Fe(III) in Acidic Sediments: Isolation of Acidiphilium cryptum JF-5 Capable of Coupling the Reduction of Fe(III) to the Oxidation of Glucose
Küsel, Kirsten; Dorsch, Tanja; Acker, Georg; Stackebrandt, Erko
To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12°C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H2 was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4′,6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2.3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H2. Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic Acidiphilium
Microbial reduction of Fe(III) in acidic sediments: isolation of Acidiphilium cryptum JF-5 capable of coupling the reduction of Fe(III) to the oxidation of glucose.
Küsel, K; Dorsch, T; Acker, G; Stackebrandt, E
To evaluate the microbial populations involved in the reduction of Fe(III) in an acidic, iron-rich sediment, the anaerobic flow of supplemental carbon and reductant was evaluated in sediment microcosms at the in situ temperature of 12 degrees C. Supplemental glucose and cellobiose stimulated the formation of Fe(II); 42 and 21% of the reducing equivalents that were theoretically obtained from glucose and cellobiose, respectively, were recovered in Fe(II). Likewise, supplemental H(2) was consumed by acidic sediments and yielded additional amounts of Fe(II) in a ratio of approximately 1:2. In contrast, supplemental lactate did not stimulate the formation of Fe(II). Supplemental acetate was not consumed and inhibited the formation of Fe(II). Most-probable-number estimates demonstrated that glucose-utilizing acidophilic Fe(III)-reducing bacteria approximated to 1% of the total direct counts of 4', 6-diamidino-2-phenylindole-stained bacteria. From the highest growth-positive dilution of the most-probable-number series at pH 2. 3 supplemented with glucose, an isolate, JF-5, that could dissimilate Fe(III) was obtained. JF-5 was an acidophilic, gram-negative, facultative anaerobe that completely oxidized the following substrates via the dissimilation of Fe(III): glucose, fructose, xylose, ethanol, glycerol, malate, glutamate, fumarate, citrate, succinate, and H(2). Growth and the reduction of Fe(III) did not occur in the presence of acetate. Cells of JF-5 grown under Fe(III)-reducing conditions formed blebs, i.e., protrusions that were still in contact with the cytoplasmic membrane. Analysis of the 16S rRNA gene sequence of JF-5 demonstrated that it was closely related to an Australian isolate of Acidiphilium cryptum (99.6% sequence similarity), an organism not previously shown to couple the complete oxidation of sugars to the reduction of Fe(III). These collective results indicate that the in situ reduction of Fe(III) in acidic sediments can be mediated by heterotrophic
Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells.
Renslow, Ryan; Donovan, Conrad; Shim, Matthew; Babauta, Jerome; Nannapaneni, Srilekha; Schenk, James; Beyenal, Haluk
Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination.
Investigations on pollutant reduction in iron murd from the Schlema-Alberoda and Poehla pits
International Nuclear Information System (INIS)
Knappik, R.; Fleischer, K.; Meyer, J.
By examplary investigations with two typical iron muds from the Schlema-Alberoda and Poehla pits it was examined whether a reducing agent in flushing water is able to contribute to changes in flushing water quality by dissolution of muds. Two closed circuit apparatuses are used, in which soluted sodium dithionite as reducing agent was added periodically and the reaction progress was monitored by in-situ-measuring of redox potential and pH as well as by sampling. The experiments were planned as to apply the results for worst-case assessment. Two very different typs of mining muds regarding to their mobilizing behavior were detected. The reaction consists of the following steps: consumption of oxygen in solution, mobilization of Fe and Mn, increasing reduction of Fe(III) to Fe(II) in the solid phase. The extent of concentration change of Fe(II), Mn, As, U and other components in flushing water at conditioning as well as depending on geochemical milieu (number of reduction steps) was discussed. On experimental conditions a complete dissolution of all iron compounds is impossible even at excess of reducing agent. On the base of estimed substance potential and reaction turn-over this results may be transferred to conditions in the mines. A partial dissolution at optimal hydrodynamic conditions does not result in mobilization of pollutants (uranium, radium, arsene) but in formation of Fe(II) and Mn(II), the extent depending on potential of mud and reducing agent. The redox buffer range will not be exceeded. (orig.)
Detection and mapping of the iron ore occurrence in the sea floor sediments in the coastal zone of the Sepetiba Bay. Rio de Janeiro. Brasil
International Nuclear Information System (INIS)
Vieira, P.
This work is about the detection and mapping of the iron occurrence in the sea floor sediments in the coastal zone of the Sepetiba Bay. Rio de Janeiro. Brasil. The results of geochemical analysis revealed that the area around the mangrove forest located near the Itacuruca channel, the perpendicular direction to the Muriqui Yacht Club channel and the immediate vicinity of the the Guaiba Island Terminal were respectively the areas of highest iron ore concentration
Effects of mine drainage on the River Hayle, Cornwall. Factors affecting concentrations of copper, zinc, and iron in water, sediments and dominant invertebrate fauna
Energy Technology Data Exchange (ETDEWEB)
Brown, B.E.
Concentrations of copper, zinc and iron were measured in waters, sediments and invertebrates collected from the River Hayle. In river water at least 70% of copper and iron was associated with the ''particulate'' fraction whereas 80% of zinc was in the ''soluble'' form. Although total concentrations of zinc in water exceeded those of copper approximately ten fold, copper predominated over zinc in the sediments by a factor of approximately three. Iron was the most abundant metal recorded in both water and sediments. Seasonal differences in ''total'' metal content of waters suggested that concentrations of copper, zinc and iron increased during periods of high flow and decreased during lower flows. Copper concentrations in the sediment, unlike zinc and iron, showed markedly higher values during the summer sampling period when flows were minimal. In the ''free-living'' Trichoptera larvae, concentrations of copper and zinc in the tissue appeared to follow copper and zinc levels in the water. Similar relationships in Odonata and Plecoptera larvae were not obtained. Factors affecting animal/metal relationships are discussed with particular reference to adaptation shown by organisms exposed to high concentrations of heavy metals in their environment.
Sulphate reduction and nitrogen fixation rates associated with roots, rhizomes and sediments from Zostera noltii and Spartina maritima meadows.
Nielsen, L B; Finster, K; Welsh, D T; Donelly, A; Herbert, R A; de Wit, R; Lomstein, B A
Sulphate reduction rates (SRR) and nitrogen fixation rates (NFR) associated with isolated roots, rhizomes and sediment from the rhizosphere of the marine macrophytes Zostera noltii and Spartina maritima, and the presence and distribution of Bacteria on the roots and rhizomes, were investigated. Between 1% and 3% of the surface area of the roots and rhizomes of both macrophytes were colonized by Bacteria. Bacteria on the surfaces of S. maritima roots and rhizomes were evenly distributed, while the distribution of Bacteria on Z. noltii roots and rhizomes was patchy. Root- and rhizome-associated SRR and NFR were always higher than rates in the bulk sediment. In particular, nitrogen fixation associated with the roots and rhizomes was 41-650-fold higher than in the bulk sediment. Despite the fact that sulphate reduction was elevated on roots and rhizomes compared with bulk sediment, the contribution of plant-associated sulphate reduction to overall sulphate reduction was small (< or =11%). In contrast, nitrogen fixation associated with the roots and rhizomes accounted for 31% and 91% of the nitrogen fixed in the rhizosphere of Z. noltii and S. maritima respectively. In addition, plant-associated nitrogen fixation could supply 37-1,613% of the nitrogen needed by the sulphate-reducing community. Sucrose stimulated nitrogen fixation and sulphate reduction significantly in the root and rhizome compartments of both macrophytes, but not in the bulk sediment.
Methods for the shipboard determination of dissolved iron and manganese in samples of sediment interstitial water
International Nuclear Information System (INIS)
Hydes, D.J.; Chapman, E.
Iron is extremely unstable in the presence of oxygen. A working atmosphere containing less than 0.2% oxygen is required if iron losses are not to be significant. Iron can be determined with a single addition of reagent, either manually or by a continuous flow procedure using ferrozine. Using a continuous flow procedure with a 5 cm colorimeter cell the method is linear up to 40 μM Fe and the precision is 2%. Manganese can similarly be determined with a single reagent addition using formaldoxime. For the continuous flow procedure with a 5 cm colorimeter cell the method is linear up to 60 μM Mn and the precision is 1%; however, under these conditions a solution containing 100 μm of iron produces an interference equivalent to 4.7 μM of manganese. A two-reagent procedure was developed using EDTA to suppress the iron interference. Using a 5% EDTA solution interference from a solution containing 100 μM of iron was undetectable. (author)
Cliff R. Hupp; Michael R. Schening
Sedimentation is arguably the most important water-quality concern in the United States. Sediment trapping is cited frequently as a major function of riverine-forested wetlands, yet little is known about sedimcntation rates at the landscape scale in relation to site parameters, including woody vegetation type, elevation, velocity, and hydraulic connection to the river...
Phase change of iron ore reduction process using EFB as reducing agent at 900-1200°C
Purwanto, H.; Salleh, H. M.; Rozhan, A. N.; Mohamad, A. S.; Zakiyuddin, A.
Treatment of low grade iron ore involved reduction of oxygen in iron oxide by using reductant such as carbon monoxide or hydrogen gas. Presently, carboneous materials such as coke/coal are widely used as a source to provide reducing gas, but some problem arises from this material as the gas can harm the environments. Therefore, empty fruit bunch biomass from oil palm becomes an alternative to replace the usage of coke/coal as their major composition is carbon and hydrogen. The idea of replacing coke with biomass will reduce the amount of carbon dioxide release as biomass is a carbon neutral and renewable source, and at the same time abundance of waste from oil palm industries can be overcome. Therefore, the aim of this research is to upgrade the low grade iron with reducibility more than 50% being used in iron and steel making. In this research, low grade iron ore are mixed together with EFB then is making into composite pellet before being reduced at certain parameter chosen. The variables involved in this research is composition EFB (10%, 30% and 50%), temperature (1000°C, 1100°C and 1200°C) and reduction time is fixed with 30 minutes. From the experiment conducted, the highest reducibility achieved is 76.37% at temperature 1200°C. While XRD analysis shows the existence of metallic iron phase started to form at 1000°C with composition of 30% of EFB. Meanwhile, from magnetization test show that at 1200°C the highest magnetic susceptibility is achieved as the dominance phase at 1200°C is metallic phase. Therefore it is an interesting alternative to replace coke with biomass for reducing agent in upgrading low grade iron into workable ores.
Directory of Open Access Journals (Sweden)
N. Alavifard
Full Text Available In the present work, iron recovery from a low-grade hematite ore (containing less than 40% iron, which is not applicable in common methods of ironmaking, was studied. Non-coking coal was used as reducing agent. Reduction experiments were performed under various coal to hematite ratios and temperatures. Reduction degree was calculated using the gravimetric method. Reduced samples were subjected to magnetic separation followed by X-ray diffraction analysis. Total iron content, degree of metallization and recovery efficiency in magnetic part were determined by quantitative chemical analysis, which were obtained about 82%, 95% and 64% respectively under optimal conditions. CaO as an additive improved ore reducibility and separation efficiency. The microstructure of reduced samples and final products were analyzed by scanning electron microscopy. Final product with a high degree of metallization can be used in steel making furnaces and charging of blast furnaces which can improve production efficiency and decrease coke usage.
Influence of dihydroxybenzenes on paracetamol and ciprofloxacin degradation and iron(III) reduction in Fenton processes.
Costa E Silva, Beatriz; de Lima Perini, João Angelo; Nogueira, Raquel F Pupo
The degradation of paracetamol (PCT) and ciprofloxacin (CIP) was compared in relation to the generation of dihydroxylated products, Fe(III) reduction and reaction rate in the presence of dihydroxybenzene (DHB) compounds, or under irradiation with free iron (Fe 3+ ) or citrate complex (Fecit) in Fenton or photo-Fenton process. The formation of hydroquinone (HQ) was observed only during PCT degradation in the dark, which increased drastically the rate of PCT degradation, since HQ formed was able to reduce Fe 3+ and contributed to PCT degradation efficiency. When HQ was initially added, PCT and CIP degradation rate in the dark was much higher in comparison to the absence of HQ, due to the higher and faster formation of Fe 2+ at the beginning of reaction. In the absence of HQ, no CIP degradation was observed; however, when HQ was added after 30 min, the degradation rate increased drastically. Ten PCT hydroxylated intermediates were identified in the absence of HQ, which could contribute for Fe(III) reduction and consequently to the degradation in a similar way as HQ. During CIP degradation, only one product of hydroxyl radical attack on benzene ring and substitution of the fluorine atom was identified when HQ was added to the reaction medium.
Effect of Ca-Fe oxides additives on NOx reduction in iron ore sintering
Institute of Scientific and Technical Information of China (English)
Zhi-yuan Yu; Xiao-hui Fan; Min Gan; Xu-ling Chen
As the emission control regulations get stricter, the NOx reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain. The NOx emissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus, it is essential to reduce NOx emissions from the sintering machine, for the achievement of clean production of sinter.Ca-Fe oxides, serving as the main binding phase in the sinter, are therefore used as additives into the sintering mixture to reduce NOx emissions.The results show that the NOx re-duction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ig-nition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile, the exist-ence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point com-pounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8% since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines, inhibiting the mineralization reaction of sintering mixture.Additionally, the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of -0.5 mm and 0.5-3.0 mm in size.
Iron Mineralogy and Speciation in Clay-Sized Fractions of Chinese Desert Sediments
Lu, Wanyi; Zhao, Wancang; Balsam, William; Lu, Huayu; Liu, Pan; Lu, Zunli; Ji, Junfeng
Iron released from Asian desert dust may be an important source of bioavailable iron for the North Pacific Ocean and thereby may stimulate primary productivity. However, the Fe species of the fine dusts from this source region are poorly characterized. Here we investigate iron species and mineralogy in the clay-sized fractions (iron phases (ferrihydrite and lepidocrocite) and reducible iron oxides (dominated by goethite) are 0.81 wt % and 2.39 wt %, respectively, and Fe dissolved from phyllosilicates extracted by boiling HCl (dominated by chlorite) is 3.15 wt %. Dusts originating from deserts in northwestern China, particularly the Taklimakan desert, are relatively enriched in easily reducible Fe phases, probably due to abundant Fe contained in fresh weathering products resulting from the rapid erosion associated with active uplift of mountains to the west. Data about Fe speciation and mineralogy in Asian dust sources will be useful for improving the quantification of soluble Fe supplied to the oceans, especially in dust models.
Evolution of the near-UV emission spectrum associated with the reduction process in microwave iron making.
Matsubara, Akihiro; Takayama, Sadatsugu; Okajima, Shigeki; Sato, Motoyasu
The structure of the emission spectrum in the near-UV range (240 nm-310 nm) changes drastically from the continuous spectrum to a discrete line spectrum with increasing sample temperature during the carbothermic reduction of magnetite in a 2.45 GHz microwave multimode furnace. The continuous spectrum can be assigned as a cathodoluminescence of magnetite. The dynamic evolution of the spectrum from continuous to discrete represents the progress of the reduction from magnetite to iron.
Comparative study of reactions between µ-nitrido- or µ-oxo-bridged iron tetrasulfophthalocyanines and sulfur-containing reductants
Directory of Open Access Journals (Sweden)
Dereven'kov Ilia A.
Full Text Available A comparative study of reactivity of μ-nitrido- and μ-oxo-dimers of iron tetrasulfophthalocyanine has been performed in aqueous solutions of various acidity. The substantially higher stability of nitrido-bridged structure under both strongly acidic and strongly alkaline environments was demonstrated. Reactions of the complexes with sulfur-containing reductants (sodium dithionite, thiourea dioxide, sodium hydroxymethanesulfinate, L-cysteine has been studied. Differences in reduction processes were explained.
Synthesis of iron nanoparticles with poly(1-vinylpyrrolidone-co-vinyl acetate) and its application to nitrate reduction
DEFF Research Database (Denmark)
Lee, Nara; Choi, Kyunghoon; Uthuppu, Basil
This study aimed to synthesize dispersed and reactive nanoscale zero-valent iron (nZVI) with poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA), nontoxic and biodegradable stabilizer. The nZVI used for the experiments was prepared by reduction of ferric solution in the presence of PVP/VA with spe...
Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6
Energy Technology Data Exchange (ETDEWEB)
Dr Robin Gerlach; Erin K. Field; Sridhar Viamajala; Brent M. Peyton; William A. Apel; Al B. Cunningham
Microbially reduced iron minerals can reductively transform a variety of contaminants including heavy metals, radionuclides, chlorinated aliphatics, and nitroaromatics. A number of Cellulomonas spp. strains, including strain ES6, isolated from aquifer samples obtained at the U.S. Department of Energy's Hanford site in Washington, have been shown to be capable of reducing Cr(VI), TNT, natural organic matter, and soluble ferric iron [Fe(III)]. This research investigated the ability of Cellulomonas sp. strain ES6 to reduce solid phase and dissolved Fe(III) utilizing different carbon sources and various electron shuttling compounds. Results suggest that Fe(III) reduction by and growth of strain ES6 was dependent upon the type of electron donor, the form of iron present, and the presence of synthetic or natural organic matter, such as anthraquinone-2,6-disulfonate (AQDS) or humic substances. This research suggests that Cellulomonas sp. strain ES6 could play a significant role in metal reduction in the Hanford subsurface and that the choice of carbon source and organic matter addition can allow for independent control of growth and iron reduction activity.
Microbial Oxidation of Pyrite Coupled to Nitrate Reduction in Anoxic Groundwater Sediment
DEFF Research Database (Denmark)
Jørgensen, Christian Juncher; Elberling, Bo; Jacobsen, Ole Stig
denitrification process with pyrite as the primary electron donor. The process demonstrates a temperature dependency (Q10) of 1.8 and could be completely inhibited by addition of a bactericide (NaN3). Experimentally determined denitrification rates show that more than 50% of the observed nitrate reduction can...... be ascribed to pyrite oxidation. The apparent zero-order denitrification rate in anoxic pyrite containing sediment at groundwater temperature has been determined to be 2-3 µmol NO3- kg-1 day-1. The in situ groundwater chemistry at the boundary between the redoxcline and the anoxic zone reveals that between 65......-anoxic boundary in sandy aquifers thus determining the position and downward progression of the redox boundary between nitrate-containing and nitrate-free groundwater....
Iron alloy Fischer-tropsch catalysts--1. Oxidation-reduction studies of the Fe-Ni system
Energy Technology Data Exchange (ETDEWEB)
Unmuth, E.E.; Schwartz, L.H.; Butt, J.B.
Catalysts containing 5% iron, nickel, or 4:1 iron-nickel on silica were hydrogen-reduced at 425/sup 0/C for 12 or 24 hr, reoxidized in air for 2 or 4 hr, reduced again in hydrogen for 12 hr, and studied at each treatment step by Moessbauer spectroscopy, X-ray diffraction, and temperature-programed desorption. The nickel was reduced directly to the metal, redispersed during the oxidation, and gave 20% smaller particles in the second reduction than in the first reduction. The ..cap alpha..-Fe/sub 2/O/sub 3/ reduced via an Fe/sub 3/O/sub 4/ intermediate and yielded approx. 70% metallic iron and the second reduction produced about the same particle size as the first reduction. The alloy catalyst reduced into a mixture of two phases, a face-centered cubic phase containing approx. 37.5% Ni, i.e., the bulk equilibrium value, and a body-centered cubic phase, and the particle sizes obtained in the first and second reductions were similar. The activation energies for the reduction were determined.
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
Energy Technology Data Exchange (ETDEWEB)
Zhang, Hanguang [Department; Hwang, Sooyeon [Center; Wang, Maoyu [School; Feng, Zhenxing [School; Karakalos, Stavros [Department; Luo, Langli [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Qiao, Zhi [Department; Xie, Xiaohong [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wang, Chongmin [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Su, Dong [Center; Shao, Yuyan [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Wu, Gang [Department
To significantly reduce the cost of proton exchange membrane (PEM) fuel cells, current Pt must be replaced by platinum-metal-group (PGM)-free catalysts for the oxygen reduction reaction (ORR) in acid. We report here a new class of high-performance atomic iron dispersed carbon catalysts through controlled chemical doping of iron ions into zinc-zeolitic imidazolate framework (ZIF), a type of metal-organic framework (MOF). The novel synthetic chemistry enables accurate size control of Fe-doped ZIF catalyst particles with a wide range from 20 to 1000 nm without changing chemical properties, which provides a great opportunity to increase the density of active sites that is determined by the particle size. We elucidated the active site formation mechanism by correlating the chemical and structural changes with thermal activation process for the conversion from Fe-N4 complex containing hydrocarbon networks in ZIF to highly active FeNx sites embedded into carbon. A temperature of 800oC was identified as the critical point to start forming pyridinic nitrogen doping at the edge of the graphitized carbon planes. Further increasing heating temperature to 1100oC leads to increase of graphitic nitrogen, generating possible synergistic effect with FeNx sites to promote ORR activity. The best performing catalyst, which has well-defined particle size around 50 nm and abundance of atomic FeNx sites embedded into carbon structures, achieve a new performance milestone for the ORR in acid including a half-wave potential of 0.85 V vs RHE and only 20 mV loss after 10,000 cycles in O2 saturated H2SO4 electrolyte. The new class PGM-free catalyst with approaching activity to Pt holds great promise for future PEM fuel cells.
Nitrogen-doped graphene-wrapped iron nanofragments for high-performance oxygen reduction electrocatalysts
Energy Technology Data Exchange (ETDEWEB)
Lee, Jang Yeol [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Na Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Shin, Dong Yun [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Park, Hee-Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Lee, Sang-Soo [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Joon Kwon, S. [Korea Institute of Science and Technology, Nanophotonics Research Center (Korea, Republic of); Lim, Dong-Hee [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Bong, Ki Wan [Korea University, Department of Chemical and Biological Engineering (Korea, Republic of); Son, Jeong Gon, E-mail: email@example.com [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Jin Young, E-mail: firstname.lastname@example.com [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of)
Transition metals, such as iron (Fe)- or cobalt (Co)-based nanomaterials, are promising electrocatalysts for oxygen reduction reactions (ORR) in fuel cells due to their high theoretical activity and low cost. However, a major challenge to using these metals in place of precious metal catalysts for ORR is their low efficiency and poor stability, thus new concepts and strategies should be needed to address this issue. Here, we report a hybrid aciniform nanostructures of Fe nanofragments embedded in thin nitrogen (N)-doped graphene (Fe@N-G) layers via a heat treatment of graphene oxide-wrapped iron oxide (Fe{sub 2}O{sub 3}) microparticles with melamine. The heat treatment leads to transformation of Fe{sub 2}O{sub 3} microparticles to nanosized zero-valent Fe fragments and formation of core-shell structures of Fe nanofragments and N-doped graphene layers. Thin N-doped graphene layers massively promote electron transfer from the encapsulated metals to the graphene surface, which efficiently optimizes the electronic structure of the graphene surface and thereby triggers ORR activity at the graphene surface. With the synergistic effect arising from the N-doped graphene and Fe nanoparticles with porous aciniform nanostructures, the Fe@N-G hybrid catalyst exhibits high catalytic activity, which was evidenced by high E{sub 1/2} of 0.82 V, onset potential of 0.93 V, and limiting current density of 4.8 mA cm{sup −2} indicating 4-electron ORR, and even exceeds the catalytic stability of the commercial Pt catalyst.
Reconstruction of Extracellular Respiratory Pathways for Iron(III Reduction in Shewanella oneidensis strain MR-1
Directory of Open Access Journals (Sweden)
Dan eCoursolle
Full Text Available Shewanella oneidensis strain MR-1 is a facultative anaerobic bacterium capable of respiring a multitude of electron acceptors, many of which require the Mtr respiratory pathway. The core Mtr respiratory pathway includes a periplasmic c-type cytochrome (MtrA, an integral outer membrane β-barrel protein (MtrB and an outer membrane-anchored c-type cytochrome (MtrC. Together, these components facilitate transfer of electrons from the c-type cytochrome CymA in the cytoplasmic membrane to electron acceptors at and beyond the outer membrane. The genes encoding these core proteins have paralogs in the S. oneidensis genome (mtrB and mtrA each have four while mtrC has three and some of the paralogs of mtrC and mtrA are able to form functional Mtr complexes. We demonstrate that of the additional three mtrB paralogs found in the S. oneidensis genome, only MtrE can replace MtrB to form a functional respiratory pathway to soluble iron(III citrate. We also evaluate which mtrC / mtrA paralog pairs (a total of 12 combinations are able to form functional complexes with endogenous levels of mtrB paralog expression. Finally, we reconstruct all possible functional Mtr complexes and test them in a S. oneidensis mutant strain where all paralogs have been eliminated from the genome. We find that each combination tested with the exception of MtrA / MtrE / OmcA is able to reduce iron(III citrate at a level significantly above background. The results presented here have implications towards the evolution of anaerobic extracellular respiration in Shewanella and for future studies looking to increase the rates of substrate reduction for water treatment, bioremediation, or electricity production.
Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.
Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne
Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.
Dissimilatory Sb(V) reduction by microorganisms isolated from Sb-contaminated sediment
Dovick, M. A.; Kulp, T. R.
Mining and smelting are major sources of trace metal contamination in freshwater systems. Arsenic (As) is a common contaminant derived from certain mining operations and is a known toxic metalloid and carcinogen. Antimony (Sb) is listed as a pollutant of priority interest by the EPA and is presumed to share similar geochemical and toxicological properties with arsenic. Both elements can occur in four different oxidation states (V, III, 0, and -III) under naturally occurring conditions. In aqueous solutions As(V) and Sb(V) predominate in oxygenated surface waters whereas As(III) and Sb(III) are stable in anoxic settings. Numerous studies have examined microbiological redox pathways that utilize As(V) as a terminal electron acceptor for anaerobic respiration, however there have been few studies on microbial mechanisms that may affect the biogeochemical cycling of Sb in the environment. Here we report bacterial reduction of Sb(V) to Sb(III) in anoxic enrichment cultures and bacterial isolates grown from sediment collected from an Sb contaminated pond at a mine tailings site in Idaho (total pond water Sb concentration = 235.2 +/- 136.3 ug/L). Anaerobic sediment microcosms (40 mL) were established in artificial freshwater mineral salt medium, amended with millimolar concentrations of Sb(V), acetate or lactate, and incubated at 27°C for several days. Antimony(V), lactate, and acetate concentrations were monitored during incubation by High Performance Liquid Chromatography (HPLC) and Ion Chromatography (IC). Live sediment microcosms reduced millimolar amendments of Sb(V) to Sb(III) coupled to the oxidation of acetate and lactate, while no activity occurred in killed controls. Enrichment cultures were established by serially diluting Sb(V)-reducing microcosms in mineral salt medium with Sb(V) and acetate, and a Sb(V)-reducing bacterial strain was isolated by plating on anaerobic agar plates amended with millimolar Sb(V) and acetate. Direct cell counting demonstrated that
A detailed study on the transition from the blocked to the superparamagnetic state of reduction-precipitated iron oxide nanoparticles
International Nuclear Information System (INIS)
Witte, K.; Bodnar, W.; Mix, T.; Schell, N.; Fulda, G.; Woodcock, T.G.; Burkel, E.
Magnetic iron oxide nanoparticles were prepared by salt-assisted solid-state chemical precipitation method with alternating fractions of the ferric iron content. The physical properties of the precipitated nanoparticles mainly consisting of magnetite were investigated by means of transmission electron microscopy, high energy X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopy. With particle sizes ranging from 16.3 nm to 2.1 nm, a gradual transition from the blocked state to the superparamagnetic state was observed. The transition was described as a dependence of the ferric iron content used during the precipitation. Composition, mean particle size, coercivity, saturation polarisation, as well as hyperfine interaction parameters and their evolution were studied systematically over the whole series of iron oxide nanoparticles. - Highlights: • Study of superparamagnetic transition of magnetite varying ferric iron content. • Coercivity is mainly influenced by the particle size. • Saturation polarisation influenced by the goethite content and the particle size. • Number of vacancies tend to increase with increasing ferric iron content. • Fe 3 O 4 B-sites are stronger effected by the reduction of particle size than A-sites.
Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center
Energy Technology Data Exchange (ETDEWEB)
Burgos, W.D.
This report summarizes research conducted in conjunction with a project entitled "Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center", which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.
Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments.
Directory of Open Access Journals (Sweden)
Arpita eBose
Full Text Available Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2-C5 and longer alkanes. C2-C4 alkanes such as ethane, propane and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1-C4 then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist. Changes in the δ13C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4‰ and 4.5‰ respectively. The concurrent depletion in the δ13C of dissolved inorganic carbon (DIC implies a transfer of carbon from the alkane to the DIC pool (-3.5 and -6.7‰ for C3 and C4 incubations, respectively. Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1-C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3-C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial community
Geochemical control on the reduction of U(VI) to mononuclear U(IV) species in lacustrine sediments
Stetten, L.; Mangeret, A.; Brest, J.; Seder-Colomina, M.; Le Pape, P.; Ikogou, M.; Zeyen, N.; Thouvenot, A.; Julien, A.; Alcalde, G.; Reyss, J. L.; Bombled, B.; Rabouille, C.; Olivi, L.; Proux, O.; Cazala, C.; Morin, G.
Contaminated systems in which uranium (U) concentrations slightly exceed the geochemical background are of particular interest to identify natural processes governing U trapping and accumulation in Earth's surface environments. For this purpose, we examined the role of early diagenesis on the evolution of U speciation and mobility in sediments from an artificial lake located downstream from a former mining site. Sediment and pore water chemistry together with U and Fe solid state speciation were analyzed in sediment cores sampled down to 50 cm depth at four locations in the lake. These organic-rich sediments (∼12% organic C) exhibited U concentrations in the 40-80 mg kg-1 range. The sediment columns were anoxic 2-3 mm below the sediment-water interface and pore waters pH was circumneutral. Pore water chemistry profiles showed that organic carbon mineralization was associated with Fe and Mn reduction and was correlated with a decrease in dissolved U concentration with depth. Immobilization of U in the sediment was correlated with the reduction of U(VI) to U(IV) at depth, as shown by U LIII-edge XANES spectroscopic analysis. XANES and EXAFS spectroscopy at the Fe K-edge showed the reduction of structural Fe(III) to Fe(II) in phyllosilicate minerals with depth, coincident with U(VI) to U(IV) reduction. Thermodynamic modeling suggests that Fe(II) could act as a major reducing agent for U(VI) during early diagenesis of these sediments, leading to complete U reduction below ∼30 cm depth. Shell-by-shell and Cauchy-Wavelet analysis of U LIII-EXAFS spectra indicates that U(VI) and U(IV) are mainly present as mononuclear species bound to C, P or Si ligands. Chemical extractions confirmed that ∼60-80% of U was present as non-crystalline species, which emphasizes that such species should be considered when evaluating the fate of U in lacustrine environments and the efficiency of sediment remediation strategies.
Sediment yield response to sediment reduction strategies implemented for 10 years in watersheds managed for industrial forestry in northern California
Kate Sullivan
For the past decade, the productive forestlands now owned and operated by the Humboldt Redwood Company have been managed with low impact practices designed to reduce sediment delivery according to voluntary agreements and regulatory requirements of state and federal agencies. These timberlands located in the erosive sedimentary terrain of the northern coast of...
Kinetics and mechanism of reduction of iron(iii) kojic acid complex by hydroquinone and l-cysteine
International Nuclear Information System (INIS)
Hussain, Z.; Perviaz, M.; Kazmi, S.A.; Johnson, A.S.; Offiong, O.E.
The effect of pH on the kinetics of reduction of iron(III) kojic acid complex by hydroquinone (H/sub 2/Q) and L-cysteine (L-Cys) was studied in the pH range of 2.34 - 4.03 for H/sub 2/Q and 3.04 - 5.5 for L-cysteine at ionic strength of 0.5 M and at 35 degree C. The pseudo-first order rate constants for the reduction of Fe(KA)3 by L-cysteine and hydroquinone increase linearly with increasing reductant concentration, indicating first-order kinetics in reductant concentration. However, whereas the rate of reduction by H2Q increases with increasing pH, an opposite trend was observed in the case of reduction by L-cysteine. Plausible rate laws and mechanisms have been proposed in line with these observations. Activation parameters (delta H no and delta S no) were evaluated for the reduction of iron (III) kojic acid complex by cysteine and the values obtained are 35.25 kJmol-1, -141.4 JK-1mol-1 and 28.14 kJmol-1 , 161.2 JK-1mol-1 for pH 4.5 and 3.52 respectively. (author)
Effectiveness of best management practices for sediment reduction at operation forest stream crossings
Laura R. Wear; Michael W. Aust; M. Chad Bolding; Brian D. Strahm; C. Andrew Dolloff
Temporary skid trail stream crossings have repeatedly been identified as having considerable potential to introduce sediment to streams. Forestry Best Management Practices (BMPs) have proven to be effective for controlling erosion and subsequent sedimentation, yet few studies have quantified sedimentation associated with various levels of BMPs for skidder stream...
Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process
International Nuclear Information System (INIS)
Chen, S.-S.; Cheng, C.-Y.; Li, C.-W.; Chai, P.-H.; Chang, Y.-M.
Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO 4 2- ) to trivalent chromium (Cr 3+ ) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH) 3(s) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr 6+ , pH 2 and ZVI dosage of 3 g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe 3+ was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe 2+ but very low Fe 3+ was present. It can be explained that ZVI reacted with chromate to produce Fe 2+ first and the presence of chromate would keep converting Fe 2+ to Fe 3+ . Therefore, Fe 2+ is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction
Identification and determination of the contribution of iron-steel manufacturing industry to sediment-associated polycyclic aromatic hydrocarbons (PAHs) in a large shallow lake of eastern China.
Zhang, Liu; Bai, Ya-Shu; Wang, Ji-Zhong; Peng, Shu-Chuan; Chen, Tian-Hu; Yin, Da-Qiang
Seventeen polycyclic aromatic hydrocarbon (PAH) compounds were determined in surface sediments collected from the Chaohu Lake (a large shallow lake in eastern China) and its tributaries. Both diagnostic ratios and a receptor model (positive matrix factorization, PMF) were applied to identify and determine the contribution of a local iron-steel manufacturing plant located in the Nanfei River (NFR) to the Chaohu Lake basin. The results show that sites located in the downstream of the steel plant contained concentrations of 17 PAH (Σ 17 PAH) approximately two orders of magnitudes higher than those from other sites. Five factors were identified by the PMF model, including industrial waste, wood/biomass burning, diagenetic origin, domestic coal combustion, and industrial combustion. Our findings suggest that sediments in the downstream of the plant and in the western part of the Chaohu Lake were predominantly affected by industrial coal combustion. A mixture of pyrolytic origins impacted urban sediments in the upstream of the plant, whereas diagenetic origins along with coal and biomass burning were suggested to influence the eastern part and rural tributaries of the lake. To assess the potential ecological risk and toxicity caused by the iron-steel plant, sediment toxicity was evaluated by the PMF model, sediment quality guideline, and toxic equivalent factors. All of the three approaches suggested PAH accumulation in the NFR sediments could produce significant adverse ecological effects and half of the sediment toxicity in the NFR may be attributed to the emissions from the iron-steel plant. Some rural locations also exhibited PAH concentrations above probable effects, most likely contributed by wood/biomass burning.
Development of Sulfidogenic Sludge from Marine Sediments and Trichloroethylene Reduction in an Upflow Anaerobic Sludge Blanket Reactor
Guerrero-Barajas, Claudia; Ordaz, Alberto; García-Solares, Selene Montserrat; Garibay-Orijel, Claudio; Bastida-González, Fernando; Zárate-Segura, Paola Berenice
The importance of microbial sulfate reduction relies on the various applications that it offers in environmental biotechnology. Engineered sulfate reduction is used in industrial wastewater treatment to remove large concentrations of sulfate along with the chemical oxygen demand (COD) and heavy metals. The most common approach to the process is with anaerobic bioreactors in which sulfidogenic sludge is obtained through adaptation of predominantly methanogenic granular sludge to sulfidogenesis. This process may take a long time and does not always eliminate the competition for substrate due to the presence of methanogens in the sludge. In this work, we propose a novel approach to obtain sulfidogenic sludge in which hydrothermal vents sediments are the original source of microorganisms. The microbial community developed in the presence of sulfate and volatile fatty acids is wide enough to sustain sulfate reduction over a long period of time without exhibiting inhibition due to sulfide. This protocol describes the procedure to generate the sludge from the sediments in an upflow anaerobic sludge blanket (UASB) type of reactor. Furthermore, the protocol presents the procedure to demonstrate the capability of the sludge to remove by reductive dechlorination a model of a highly toxic organic pollutant such as trichloroethylene (TCE). The protocol is divided in three stages: (1) the formation of the sludge and the determination of its sulfate reducing activity in the UASB, (2) the experiment to remove the TCE by the sludge, and (3) the identification of microorganisms in the sludge after the TCE reduction. Although in this case the sediments were taken from a site located in Mexico, the generation of a sulfidogenic sludge by using this procedure may work if a different source of sediments is taken since marine sediments are a natural pool of microorganisms that may be enriched in sulfate reducing bacteria. PMID:26555802
Development of Sulfidogenic Sludge from Marine Sediments and Trichloroethylene Reduction in an Upflow Anaerobic Sludge Blanket Reactor.
Guerrero-Barajas, Claudia; Ordaz, Alberto; García-Solares, Selene Montserrat; Garibay-Orijel, Claudio; Bastida-González, Fernando; Zárate-Segura, Paola Berenice
The importance of microbial sulfate reduction relies on the various applications that it offers in environmental biotechnology. Engineered sulfate reduction is used in industrial wastewater treatment to remove large concentrations of sulfate along with the chemical oxygen demand (COD) and heavy metals. The most common approach to the process is with anaerobic bioreactors in which sulfidogenic sludge is obtained through adaptation of predominantly methanogenic granular sludge to sulfidogenesis. This process may take a long time and does not always eliminate the competition for substrate due to the presence of methanogens in the sludge. In this work, we propose a novel approach to obtain sulfidogenic sludge in which hydrothermal vents sediments are the original source of microorganisms. The microbial community developed in the presence of sulfate and volatile fatty acids is wide enough to sustain sulfate reduction over a long period of time without exhibiting inhibition due to sulfide. This protocol describes the procedure to generate the sludge from the sediments in an upflow anaerobic sludge blanket (UASB) type of reactor. Furthermore, the protocol presents the procedure to demonstrate the capability of the sludge to remove by reductive dechlorination a model of a highly toxic organic pollutant such as trichloroethylene (TCE). The protocol is divided in three stages: (1) the formation of the sludge and the determination of its sulfate reducing activity in the UASB, (2) the experiment to remove the TCE by the sludge, and (3) the identification of microorganisms in the sludge after the TCE reduction. Although in this case the sediments were taken from a site located in Mexico, the generation of a sulfidogenic sludge by using this procedure may work if a different source of sediments is taken since marine sediments are a natural pool of microorganisms that may be enriched in sulfate reducing bacteria.
Immobilization of mercury in field soil and sediment using carboxymethyl cellulose stabilized iron sulfide nanoparticles
Gong, Yanyan; Liu, Yuanyuan; Xiong, Zhong; Kaback, Dawn; Zhao, Dongye
Mercury (Hg) is one of the most pervasive and bio-accumulative metals in the environment. Yet, effective in situ remediation technologies have been lacking. This study investigated the effectiveness of a class of soil-deliverable FeS nanoparticles for in situ immobilization of Hg in two field-contaminated soils from a New Jersey site and one sediment from an Alabama site. The nanoparticles were prepared using sodium carboxymethyl cellulose (CMC) as a stabilizer. Transmission electron microscopy measurements revealed a particle size of 34.3 ± 8.3 nm (standard deviation), whereas dynamic light scattering gave a hydrodynamic diameter of 222.5 ± 3.2 nm. Batch tests showed that at an FeS-to-Hg molar ratio of 28:1-118:1, the nanoparticles reduced water-leachable Hg by 79%-96% and the TCLP (toxicity characteristic leaching procedure) based leachability by 26%-96%. Column breakthrough tests indicated that the nanoparticles were deliverable in the sediment/soil columns under moderate injection pressure. However, once the external pressure was removed, the delivered nanoparticles remained virtually mobile under typical groundwater flow conditions. When the Hg-contaminated soil and sediment were treated with 52-95 pore volumes of a 500 mg l-1 FeS nanoparticle suspension, water-leachable Hg was reduced by 90%-93% and TCLP-leachable Hg was reduced by 65%-91%. The results warrant further field demonstration of this promising in situ remediation technology.
Microbial Mn(IV) and Fe(III) reduction in northern Barents Sea sediments under different conditions of ice cover and organic carbon deposition
DEFF Research Database (Denmark)
Nickel, Maren; Vandieken, Verona; Brüchert, Volker
station, with seasonally extended ice cover, low organic carbon content and sedimentation rate combined with relatively high concentrations of Mn and Fe(III) oxides favored dissimilatory Fe and Mn reduction (98% of anaerobic carbon oxidation) over sulfate reduction in the top 12 cm of the sediment....... In contrast, in a sediment that had not been ice covered for at least 12 months and with more organic carbon and a higher sedimentation rate, sulfate reduction was the most important anaerobic electron-accepting process (>80% of anaerobic carbon oxidation). In the upper 3 cm, microbial Fe and sulfate...
Reduction enhances yields of nitric oxide trapping by iron-diethyldithiocarbamate complex in biological systems.
Vanin, A.F.; Bevers, L.M.; Mikoyan, V.D.; Poltorakov, A.P.; Kubrina, L.N.; Faassen, E. van
The mechanism of NO trapping by iron-diethylthiocarbamate complexes was investigated in cultured cells and animal and plant tissues. Contrary to common belief, the NO radicals are trapped by iron-diethylthiocarbamates not only in ferrous but in ferric state also in the biosystems. When DETC was
Microbial iron reduction related to metal speciation in mine waste at the former uranium mine in Ranstad
International Nuclear Information System (INIS)
Nejad, F.T.
Mining activities in Ranstad uranium mine started in 1965 and ended in 1969. In 1988 the final restoration was discussed, and it was proposed to water-fill the open pit and cover the waste disposal area using the 'dry method'. Today the open pit has become a lake. Also some alum shale was placed on the land surface where it has been weathered by oxygen and water during 30 years. In 1994 it was observed that the color of the lake turned over to brown-red. Further studies showed increasing iron concentration in the lake and around the tailings area. For estimation of microbial iron reduction in the lake, three iron reducing bacteria were isolated from the water-filled open pit. For the enrichment process, water samples were inoculated in an anoxic enrichment medium. The isolates were able to reduce Fe(III) oxyhydroxide by oxidation of lactate as energy source. Growth of these strains was determined by production of a black precipitation of iron sulfide and was confirmed by estimation of total number of cells. Fe(III) reduction was monitored by measuring the accumulation of Fe(II) over time. Comparison of the 16S rRNA gene sequences of strains Tran-l, Tran-2, and Tran-3 with the EMBL data base showed 98.6% identity with Shewanella putrefaciens, 98.7% identity with Shewanella alga and 98.2% identity with Aeromonas salmonicida, respectively. S. putrefaciens strains have been isolated from many different environments, many of which are suboxic or anoxic. In addition to growing aerobically, S. putrefaciens can use Fe(III) as terminal electron acceptor under anaerobic conditions. To distinguish if the Fe(III) and/or organic compounds presence in weathered alum shale can be utilized by iron reducing bacteria isolated from the lake, reduction of Fe(III) coupled to the oxidation of organic compounds in sterile and non-sterile weathered alum shale was studied. The reduction of Fe(III) coupled to growth of bacteria on sterile and non-sterile shale was observed. Furthermore
Microbial iron reduction related to metal speciation in mine waste at the former uranium mine in Ranstad
Energy Technology Data Exchange (ETDEWEB)
Nejad, F.T. [Goeteborg Univ. (Sweden). Dept. of General and Marine Microbiology
Mining activities in Ranstad uranium mine started in 1965 and ended in 1969. In 1988 the final restoration was discussed, and it was proposed to water-fill the open pit and cover the waste disposal area using the `dry method`. Today the open pit has become a lake. Also some alum shale was placed on the land surface where it has been weathered by oxygen and water during 30 years. In 1994 it was observed that the color of the lake turned over to brown-red. Further studies showed increasing iron concentration in the lake and around the tailings area. For estimation of microbial iron reduction in the lake, three iron reducing bacteria were isolated from the water-filled open pit. For the enrichment process, water samples were inoculated in an anoxic enrichment medium. The isolates were able to reduce Fe(III) oxyhydroxide by oxidation of lactate as energy source. Growth of these strains was determined by production of a black precipitation of iron sulfide and was confirmed by estimation of total number of cells. Fe(III) reduction was monitored by measuring the accumulation of Fe(II) over time. Comparison of the 16S rRNA gene sequences of strains Tran-l, Tran-2, and Tran-3 with the EMBL data base showed 98.6% identity with Shewanella putrefaciens, 98.7% identity with Shewanella alga and 98.2% identity with Aeromonas salmonicida, respectively. S. putrefaciens strains have been isolated from many different environments, many of which are suboxic or anoxic. In addition to growing aerobically, S. putrefaciens can use Fe(III) as terminal electron acceptor under anaerobic conditions. To distinguish if the Fe(III) and/or organic compounds presence in weathered alum shale can be utilized by iron reducing bacteria isolated from the lake, reduction of Fe(III) coupled to the oxidation of organic compounds in sterile and non-sterile weathered alum shale was studied. The reduction of Fe(III) coupled to growth of bacteria on sterile and non-sterile shale was observed. Furthermore
Reduction of non-point source contaminants associated with road-deposited sediments by sweeping.
Kim, Do-Gun; Kang, Hee-Man; Ko, Seok-Oh
Road-deposited sediments (RDS) on an expressway, residual RDS collected after sweeping, and RDS removed by means of sweeping were analyzed to evaluate the degree to which sweeping removed various non-point source contaminants. The total RDS load was 393.1 ± 80.3 kg/km and the RDS, residual RDS, and swept RDS were all highly polluted with organics, nutrients, and metals. Among the metals studied, Cu, Zn, Pb, Ni, Ca, and Fe were significantly enriched, and most of the contaminants were associated with particles within the size range from 63 μm to 2 mm. Sweeping reduced RDS and its associated contaminants by 33.3-49.1% on average. We also measured the biological oxygen demand (BOD) of RDS in the present work, representing to our knowledge the first time that this has been done; we found that RDS contains a significant amount of biodegradable organics and that the reduction of BOD by sweeping was higher than that of other contaminants. Significant correlations were found between the contaminants measured, indicating that the organics and the metals originated from both exhaust and non-exhaust particles. Meanwhile, the concentrations of Cu and Ni were higher in 63 μm-2 mm particles than in smaller particles, suggesting that some metals in RDS likely exist intrinsically in particles, rather than only as adsorbates on particle surfaces. Overall, the results in this study showed that sweeping to collect RDS can be a good alternative for reduction of contaminants in runoff.
Enhanced phosphorus reduction in simulated eutrophic water: a comparative study of submerged macrophytes, sediment microbial fuel cells, and their combination.
Xu, Peng; Xiao, Enrong; Xu, Dan; Li, Juan; Zhang, Yi; Dai, Zhigang; Zhou, Qiaohong; Wu, Zhenbin
The phosphorus reduction in water column was attempted by integrating sediment microbial fuel cells (SMFCs) with the submerged macrophyte Vallisneria spiralis. A comparative study was conducted to treat simulated water rich in phosphate with a control and three treatments: SMFC alone (SMFC), submerged macrophytes alone (macophyte), and combined macrophytes and fuel cells (M-SMFC). All treatments promoted phosphorus flux from the water column to sediments. Maximum phosphorus reduction was obtained in proportion to the highest stable phosphorus level in sediments in M-SMFC. For the initial phosphate concentrations of 0.2, 1, 2, and 4 mg/L, average phosphate values in the overlying water during four phases decreased by 33.3% (25.0%, 8.3%), 30.8% (5.1%, 17.9%), 36.5% (27.8%, 15.7%), and 36.2% (0.7%, 22.1%) for M-SMFC (macrophyte, SMFC), compared with the control. With macrophyte treatment, the obvious phosphorus release from sediments was observed during the declining period. However, such phenomenon was significantly inhibited with M-SMFC. The electrogenesis bacteria achieved stronger phosphorus adsorption and assimilation was significantly enriched on the closed-circuit anodes. The higher abundance of Geobacter and Pseudomonas in M-SMFC might in part explain the highest phosphorus reduction in the water column. M-SMFC treatment could be promising to control the phosphorus in eutrophic water bodies.
Transformation impacts of dissolved and solid phase Fe(II) on trichloroethylene (TCE) reduction in an iron-reducing bacteria (IRB) mixed column system: a mathematical model.
Bae, Yeunook; Kim, Dooil; Cho, Hyun-Hee; Singhal, Naresh; Park, Jae-Woo
In this research, we conducted trichloroethylene (TCE) reduction in a column filled with iron and iron-reducing bacteria (IRB) and developed a mathematical model to investigate the critical reactions between active species in iron/IRB/contaminant systems. The formation of ferrous iron (Fe(II)) in this system with IRB and zero-valent iron (ZVI, Fe(0)) coated with a ferric iron (Fe(III)) crust significantly affected TCE reduction and IRB respiration in various ways. This study presents a new framework for transformation property and reducing ability of both dissolved (Fe(II)(dissolved)) and solid form ferrous iron (Fe(II)(solid)). Results showed that TCE reduction was strongly depressed by Fe(II)(solid) rather than by other inhibitors (e.g., Fe(III) and lactate), suggesting that Fe(II)(solid) might reduce IRB activation due to attachment to IRB cells. Newly exposed Fe(0) from the released Fe(II)(dissolved) was a strong contributor to TCE reduction compared to Fe(II)(solid). In addition, our research confirmed that less Fe(II)(solid) production strongly supported long-term TCE reduction because it may create an easier TCE approach to Fe(0) or increase IRB growth. Our findings will aid the understanding of the contributions of iron media (e.g., Fe(II)(solid), Fe(II)(dissolved), Fe(III), and Fe(0)) to IRB for decontamination in natural groundwater systems. Copyright © 2012 Elsevier Ltd. All rights reserved.
Synthesis and characterization of β-phase iron silicide nano-particles by chemical reduction
International Nuclear Information System (INIS)
Sen, Sabyasachi; Gogurla, Narendar; Banerji, Pallab; Guha, Prasanta K.; Pramanik, Panchanan
Graphical abstract: - Highlights: • β-FeSi 2 nano-particle was synthesized by reducing with Mg and by diluting with MgO. • XRD profile shows the iron di-silicide phase to be semiconducting β-FeSi 2 . • HRTEM and FESEM images indicate the β-FeSi 2 average particle size to be 60–70 nm. • Absorption, reflectance and PL spectroscopy show band gap to be direct 0.87 eV. • Nano-β-FeSi 2 is p-type with hole density of 4.38 × 10 18 cm −3 and mobility 8.9 cm 2 /V s. - Abstract: Nano-particles of β-FeSi 2 have been synthesized by chemical reduction of a glassy phase of [Fe 2 O 3 , 4SiO 2 ] by Mg-metal where MgO is used as diluent to prevent the agglomeration of nano crystallites into micro-particles and also act as a negative catalyst for the formation of other phases. The sample is characterized by XRD, FESEM, HRTEM, EDX, ultra-violet-visible-infrared and PL spectroscopy and electronic properties have been investigated by Hall measurement. XRD profile shows that the synthesized powder consists of purely β-FeSi 2 semiconducting phase. The average crystallite size of β-FeSi 2 is determined to be around 65.4 nm from XRD peaks as well as from FESEM also. The optical absorption and PL spectroscopy shows that synthesized β-FeSi 2 phase is a direct band gap semiconductor with a value of 0.87 eV. Hall measurements show that β-FeSi 2 nano-particles is p-type with hole concentration of 4.38 × 10 18 cm −3 and average hole mobility of 8.9 cm 2 /V s at 300 K
Reduction and immobilization of chromate in chromite ore processing residue with nanoscale zero-valent iron
International Nuclear Information System (INIS)
Du, Jingjing; Lu, Jinsuo; Wu, Qiong; Jing, Chuanyong
Highlights: ► COPR remediation mechanism using nZVI was investigated. ► PHREEQC model calculation agreed well with our GANC experimental results. ► Incubation COPR and nZVI with >27% water content could reduce Cr(VI) in solids. ► Water content is the key factor to assist electron transfer between nZVI and COPR. - Abstract: Chromite ore processing residue (COPR) poses a great environmental and health risk with persistent Cr(VI) leaching. To reduce Cr(VI) and subsequently immobilize in the solid matrix, COPR was incubated with nanoscale zero-valent iron (nZVI) and the Cr(VI) speciation and leachability were studied. Multiple complementary analysis methods including leaching tests, X-ray powder diffraction, X-ray absorption near edge structure (XANES) spectroscopy, and X-ray photoelectron spectroscopy (XPS) were employed to investigate the immobilization mechanism. Geochemical PHREEQC model calculation agreed well with our acid neutralizing capacity experimental results and confirmed that when pH was lowered from 11.7 to 7.0, leachate Cr(VI) concentrations were in the range 358–445 mg L −1 which contributed over 90% of dissolved Cr from COPR. Results of alkaline digestion, XANES, and XPS demonstrated that incubation COPR with nZVI under water content higher than 27% could result in a nearly complete Cr(VI) reduction in solids and less than 0.1 mg L −1 Cr(VI) in the TCLP leachate. The results indicated that remediation approaches using nZVI to reduce Cr(VI) in COPR should be successful with sufficient water content to facilitate electron transfer from nZVI to COPR.
Enhanced terrestrial carbon preservation promoted by reactive iron in deltaic sediments
Shields, Michael R.; Bianchi, Thomas S.; Gélinas, Yves; Allison, Mead A.; Twilley, Robert R.
We examined the role of reactive iron (FeR) in preserving organic carbon (OC) across a subaerial chronosequence of the Wax Lake Delta, a prograding delta within the Mississippi River Delta complex. We found that ~15.0% of the OC was bound to FeR, and the dominant binding mechanisms varied from adsorption in the youngest subaerial region to coprecipitation at the older, vegetated sites. The δ13C of the iron-associated OC was more negative than the total OC (mean = -2.6‰), indicating greater preference for terrestrial material and/or compounds with more negative δ13C values. However, only the adsorbed OC displayed preferential binding of lignin phenols. We estimate that ~8% of the OC initially deposited in deltaic systems is bound to FeR (equivalent to 6 × 1012 gC yr-1), and this percentage increases postdepositionally, as coprecipitation of FeR and OC allows for an even greater amount of OC to be bound to FeR.
The reduction of U(VI) on corroded iron under anoxic conditions
International Nuclear Information System (INIS)
Cui, D.; Spahiu, K.
The corrosion of iron and the interaction between corroded iron and U(VI) in anoxic conditions were investigated. The anoxic conditions were obtained by flushing an 99.97% Ar-0.03% CO 2 gas mixture through the test vessel, in which an oxygen trap and six reaction bottles containing synthetic groundwater (10 mM NaCl and 2 mM HCO 3 - .) were placed. The dark-green coloured corrosion product, formed on iron surface after three months corrosion in synthetic groundwater solutions, was identified by powder X-ray diffraction to be carbonate green rust, Fe 4 II Fe 2 III (OH) 12 CO 3 . The iron foil that reacted in a solution (10 ppm U(VI), 10 mM NaCl and 2 mM HCO 3 - ) for three months was analysed by SEM-EDS. The result shows that: (i) an uneven layer of carbonate green rust (1-5 μm thick) formed on the metallic iron; (ii) a thin (0.3 μm) uranium-rich layer deposited on top of the carbonate green rust layer; and (iii) some UO 2 crystals (3-5 μm sized) on the thin uranium layer. The experimental results proved that the U(VI) removal capacity of metal iron is not hindered by formation of a layer of carbonate green rust on the iron. Tests with cast iron and pure iron indicate that they have similar U(VI) removal capacities. At the end of experiment, U concentrations in solution approached the solubility of UO 2 (s), 10 -8 M. The stability of the carbonate green rust at the experimental conditions, pH, E h , [Fe 2+ ] and [HCO 3 - ], is discussed. (orig.)
Sulfate reduction in Black Sea sediments: in situ and laboratory radiotracer measurements from the shelf to 2000m depth
DEFF Research Database (Denmark)
Weber, A.; Riess, W.; Wenzhoefer, F.
anoxic basin. The highest rates measured on an areal basis for the upper 0-15 cm were 1.97 mmol m(-2) d(-1) on the shelf and 1.54 mmol m(-2) d(-1) at 181 m water depth just below the chemocline. At all stations sulfate reduction rates decreased to values 50% just above the chemocline to 100% just below...... sediments showed that the present results tend to be higher in shelf sediments and lower in the deep-sea than most other data. Based on the present water column H2S inventory and the H2S flux out of the sediment, the calculated turnover time of H2S below the chemocline is 2100 years. (C) 2001 Elsevier...
Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions
Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.
Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.
Reactivity of Uranium and Ferrous Iron with Natural Iron Oxyhydroxides.
Stewart, Brandy D; Cismasu, A Cristina; Williams, Kenneth H; Peyton, Brent M; Nico, Peter S
Determining key reaction pathways involving uranium and iron oxyhydroxides under oxic and anoxic conditions is essential for understanding uranium mobility as well as other iron oxyhydroxide mediated processes, particularly near redox boundaries where redox conditions change rapidly in time and space. Here we examine the reactivity of a ferrihydrite-rich sediment from a surface seep adjacent to a redox boundary at the Rifle, Colorado field site. Iron(II)-sediment incubation experiments indicate that the natural ferrihydrite fraction of the sediment is not susceptible to reductive transformation under conditions that trigger significant mineralogical transformations of synthetic ferrihydrite. No measurable Fe(II)-promoted transformation was observed when the Rifle sediment was exposed to 30 mM Fe(II) for up to 2 weeks. Incubation of the Rifle sediment with 3 mM Fe(II) and 0.2 mM U(VI) for 15 days shows no measurable incorporation of U(VI) into the mineral structure or reduction of U(VI) to U(IV). Results indicate a significantly decreased reactivity of naturally occurring Fe oxyhydroxides as compared to synthetic minerals, likely due to the association of impurities (e.g., Si, organic matter), with implications for the mobility and bioavailability of uranium and other associated species in field environments.
Reductive dehalogenation of polychlorinated biphenyls by anaerobic microorganisms enriched from Dutch sediments
HartkampCommandeur, LCM; Gerritse, J; Govers, HAJ; Parsons, [No Value
The dehalogenation of PCBs by anaerobic microbial cultures enriched from Dutch sediments was investigated. One mixed culture originating from estuarine sediments of the River Rhine (the Chemie Harbour), dehalogenated 2,2',3,3',4,4'- and 2,2,',3,3',6,6'-hexachlorobiphenyls (HCB) to yield penta- and
Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations
Fabisch, Maria; Beulig, Felix; Akob, Denise M.; Küsel, Kirsten
We identified and quantified abundant iron-oxidizing bacteria (FeOB) at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7), to moderately acidic (R2, pH 4.4), to slightly acidic (R3, pH 6.3) in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U) bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic "Ferrovum myxofaciens" was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and "Ferrovum myxofaciens" revealed that ~72% (R2 sediment) and 37% (R3 sediment) of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.
Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations
Directory of Open Access Journals (Sweden)
Maria eFabisch
Full Text Available We identified and quantified abundant iron-oxidizing bacteria (FeOB at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7, to moderately acidic (R2, pH 4.4, to slightly acidic (R3, pH 6.3 in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic 'Ferrovum myxofaciens' was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and 'Ferrovum myxofaciens' revealed that approximately 72% (R2 sediment and 37% (R3 sediment of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.
Spatial distribution of iron, copper and lead in mangrove sediments in a degradation gradient in Guanabara Bay (Rio de Janeiro State)
Borges, Anderson C.; Dias, Jailson C.; Machado, Wilson; Patchineelam, Sambasiva R.; Sella, Silvia M.
Iron, copper and lead distribution was evaluated in sediment cores from a disturbed mangrove area in Guanabara Bay: a core from a seaward site where mangrove vegetation was removed ~20 yr before sampling (MD); a core from an intermediate site with dead vegetation, apparently due to insect attack (MP), and a core from a landward site with living vegetation (MV). Metal concentrations showed increasing values seaward while organic matter content showed an inverse trend, displaying a negative cor...
Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium
CSIR Research Space (South Africa)
Mamuru, SA
Full Text Available Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron...
Oxygen reduction reaction at MWCNT-modified nanoscale iron(II) tetrasulfophthalocyanine: remarkable performance over platinum and tolerance toward methanol in alkaline medium
CSIR Research Space (South Africa)
Fashedemi, OO
Full Text Available A nanoscale iron(II) tetrasulfophthalocyanine (nanoFeTSPc) catalyst obtained by co-ordinating with hexadecyltrimethylammonium bromide and subsequently anchored onto multi-walled carbon nanotubes (MWCNTs) for oxygen reduction reaction (ORR) has been...
Suspended-sediment and turbidity responses to sediment and turbidity reduction projects in the Beaver Kill, Stony Clove Creek, and Warner Creek, Watersheds, New York, 2010–14
Siemion, Jason; McHale, Michael R.; Davis, Wae Danyelle
Suspended-sediment concentrations (SSCs) and turbidity were monitored within the Beaver Kill, Stony Clove Creek, and Warner Creek tributaries to the upper Esopus Creek in New York, the main source of water to the Ashokan Reservoir, from October 1, 2010, through September 30, 2014. The purpose of the monitoring was to determine the effects of suspended-sediment and turbidity reduction projects (STRPs) on SSC and turbidity in two of the three streams; no STRPs were constructed in the Beaver Kill watershed. During the study period, four STRPs were completed in the Stony Clove Creek and Warner Creek watersheds. Daily mean SSCs decreased significantly for a given streamflow after the STRPs were completed. The most substantial decreases in daily mean SSCs were measured at the highest streamflows. Background SSCs, as measured in water samples collected in upstream reference stream reaches, in all three streams in this study were less than 5 milligrams per liter during low and high streamflows. Longitudinal stream sampling identified stream reaches with failing hillslopes in contact with the stream channel as the primary sediment sources in the Beaver Kill and Stony Clove Creek watersheds.
Nafion Coated Electrodes as Voltammetric Sensors for Iron Analysis in Sediments and Pore Waters: an Example from the Lagoon of Venice
Directory of Open Access Journals (Sweden)
Emanuele Argese
Full Text Available Glassy carbon electrodes coated with Nafion are used for the ion-exchange voltammetric (IEV determination of Fe(II in the pore-waters and acidic extracts of sediments of the lagoon of Venice (Italy. The coated electrodes give reversible voltammetric signals, well resolved from background currents, which can be used for quantitative determinations. The yield of iron extracted by HCl from the sediment depends on the experimental conditions, in particular on the concentration of hydrochloric acid. By combining IEV on the acid extract with trapping and analysis of gaseous H2S evolved it is possible to obtain quantitative information both on the total content of iron dissolved by the acid attack and on the fraction of iron present in the form of acid volatile sulphides (AVS. As far as pore-waters are concerned, in this kind of samples the IEV determination of iron can be performed simply after dilution with HCl. The pore-waters here examined were sampled without alteration of their equilibrium conditions by using a suitable "in situ†sampler. IEV data obtained in samples from the lagoon of Venice (Italy show satisfactory correlation with previous results obtained using different analytical techniques.
Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH
Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.
In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in
Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells
Directory of Open Access Journals (Sweden)
Lukasz JOZWIAK
Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406
The effect of diluting ruthenium by iron in Ru{sub x}Se{sub y} catalyst for oxygen reduction
Energy Technology Data Exchange (ETDEWEB)
Delacote, Cyril [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France); CEISAM, CNRS, University of Nantes, F-44322 Nantes Cedex 3 (France); Lewera, Adam [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Pisarek, Marcin [Institute of Physical Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw (Poland); Kulesza, Pawel J. [University of Warsaw, Department of Chemistry, ul. Pasteura 1, 02-093 Warsaw (Poland); Zelenay, Piotr [Materials Physics and Applications, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Alonso-Vante, Nicolas, E-mail: firstname.lastname@example.com [Laboratory of Electrocatalysis, CNRS, University of Poitiers, F-86022 Poitiers Cedex (France)
This study has focused on the synthesis of novel oxygen reduction reaction (ORR) chalcogenide catalysts, with Ru partially replaced by Fe in a cluster-type Ru{sub x}Se{sub y}. The catalysts were obtained by thermal decomposition of Ru{sub 3}(CO){sub 12} and Fe(CO){sub 5} in the presence of Se. As indicated by the XPS data, the composition of catalyst nanoparticles depends on the solvent used (either p-xylene or dichlorobenzene). The presence of iron in synthesized catalysts has been confirmed by both EDAX and XPS. Voltammetric activation of the catalysts results in a partial removal of iron and unreacted selenium from the surface. The ORR performance of electrochemically pre-treated catalysts was evaluated using rotating disk and ring-disk electrodes in a sulfuric acid solution. No major change in the ORR mechanism relative to the Se/Ru catalyst has been observed with Fe-containing catalysts.
Reductive Degradation of Perfluorinated Compounds in Water using Mg-aminoclay coated Nanoscale Zero Valent Iron
Arvaniti, Olga S.; Hwang, Yuhoon; Andersen, Henrik Rasmus; Stasinakis, Athanasios S.; Thomaidis , Nikolaos S.; Aloupi, Maria
Perfluorinated Compounds (PFCs) are extremely persistent micropollutants that are detected worldwide. We studied the removal of PFCs (perfluorooctanoic acid; PFOA, perfluorononanoic acid; PFNA, perfluorodecanoic acid; PFDA and perfluorooctane sulfonate; PFOS) from water by different types of nanoscale zero-valent iron (nZVI). Batch experiments showed that an iron dose of 1 g•L-1 in the form of Mg-aminoclay (MgAC) coated nZVI, at an initial pH of 3.0 effectively removed 38 % to 96 % of individ...
Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6
Energy Technology Data Exchange (ETDEWEB)
Erin K. Field; Robin Gerlach; Sridhar Viamajala; Laura K. Jennings; Alfred B. Cunningham; Brent M. Peyton; William A. Apel
The reduction of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III), can be an important aspect of remediation processes at Department of Energy (DOE) and other contaminated sites. Cellulomonas species are found at several Cr(VI) contaminated and uncontaminated locations at the DOE site in Hanford, Washington. Members of this genus have demonstrated the ability to effectively reduce Cr(VI) to Cr(III) fermentatively and therefore play a potential role in hexavalent chromium remediation at this site. Batch studies were conducted with Cellulomonas sp. strain ES6 to assess the influence of various carbon sources, iron minerals, and electron shuttling compounds on Cr(VI) reduction. These chemical species are likely to be present in these terrestrial environments during in situ bioremediation. Results indicated that there were a number of interactions between these compounds that influenced Cr(VI) reduction rates. The type of carbon source as well as the type of electron shuttle present influenced Cr(VI) reduction rates. When an electron shuttle, such as anthraquinone-2,6-disulfonate (AQDS), was present in the system, reduction rates increased significantly. Biologically reduced AQDS (AHDS) reduced Cr(VI) almost instantaneously. The presence of iron minerals and their concentrations did not significantly influence Cr(VI) reduction rates. However, strain ES6 or AQDS could directly reduce surface-associated Fe(III) to Fe(II) which was capable of reducing Cr(VI) at a near instantaneous rate. These results suggest the rate limiting step in these systems is the transfer of electrons from strain ES6 to the intermediate or terminal electron acceptor whether that is Cr(VI), Fe(III), or AQDS.
Reductive dechlorination of trichloroethylene and tetrachloroethylene under aerobic conditions in a sediment column
International Nuclear Information System (INIS)
Enzien, M.V.; Picardal, F.; Hazen, T.
This study investigated the bioremediation of chlorinated solvents in a sediment column. Biodegradation potentials of trichloroethylene and tetrachloroethylene during aerobic methanotrophic biostimulation were studied at the Savannah River Site. 30 refs., 3 figs., 3 tabs
Moessbauer spectroscopic evidence for iron(III) complexation and reduction in acidic aqueous solutions of indole-3-butyric acid
International Nuclear Information System (INIS)
Kovacs, K.; Kuzmann, E.; Vertes, A.; Kamnev, A.A.; Shchelochkov, A.G.; Medzihradszky-Schweiger, H.; Mink, J.; Hungarian Academy of Sciences, Budapest
Moessbauer spectroscopic studies were carried out in acidic (pH 2.3) 57 Fe III nitrate containing aqueous solutions of indole-3-butyric acid (IBA), rapidly frozen in liquid nitrogen at various periods of time after mixing the reagents. The data obtained show that in solution in the presence of IBA, iron(III) forms a complex with a dimeric structure characterised by a quadrupole doublet, whereas without IBA under similar conditions iron(III) exhibits a broad spectral feature due to a slow paramagnetic spin relaxation which, at liquid nitrogen temperature, results in a large anomalous line broadening (or, at T = 4.2 K, in a hyperfine magnetic splitting). The spectra of 57 Fe III +IBA solutions, kept at ambient temperature under aerobic conditions for increasing periods of time before freezing, contained a gradually increasing contribution of a component with a higher quadrupole splitting. The Moessbauer parameters for that component are typical for iron(II) aquo complexes, thus showing that under these conditions gradual reduction of iron(III) occurs, so that the majority (85%) of dissolved iron(III) is reduced within 2 days. The Moessbauer parameters for the iron(III)-IBA complex in aqueous solution and in the solid state (separated from the solution by filtration) were found to be similar, which may indicate that the dissolved and solid complexes have the same composition and/or iron(III) coordination environment. For the solid complex, the data of elemental analysis suggest the following composition of the dimer: [L 2 Fe-(OH) 2 -FeL 2 ] (where L is indole-3-butyrate). This structure is also in agreement with the data of infrared spectroscopic study of the complex reported earlier, with the side-chain carboxylic group in indole-3-butyrate as a bidentate ligand. The Moessbauer parameters for the solid 57 Fe III -IBA complex at T = 80 K and its acetone solution rapidly frozen in liquid nitrogen were virtually identical, which indicates that the complex retains its
Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection
Energy Technology Data Exchange (ETDEWEB)
Ussher, Simon J. [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Milne, Angela [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Landing, William M. [Department of Oceanography, Florida State University, Tallahassee, FL 32306-4320 (United States); Attiq-ur-Rehman, Kakar [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Seguret, Marie J.M.; Holland, Toby [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Achterberg, Eric P. [National Oceanography Centre, University of Southampton, European Way, Southampton SO14 3ZH (United Kingdom); Nabi, Abdul [Department of Chemistry, University of Balochistan, Quetta (Pakistan); Worsfold, Paul J., E-mail: firstname.lastname@example.com [School of Earth, Ocean and Environmental Sciences (SEOES), University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)
A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II) + Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100 {mu}M concentrations of sulphite a reduction time of 4 h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.
Dissimilatory nitrogen reduction in intertidal sediments of a temperate estuary: small scale heterogeneity and novel nitrate-to-ammonium reducers.
Directory of Open Access Journals (Sweden)
Helen eDecleyre
Full Text Available The estuarine nitrogen cycle can be substantially altered due to anthropogenic activities resulting in increased amounts of inorganic nitrogen (mainly nitrate. In the past, denitrification was considered to be the main ecosystem process removing reactive nitrogen from the estuarine ecosystem. However, recent reports on the contribution of dissimilatory nitrate reduction to ammonium (DNRA to nitrogen removal in these systems indicated a similar or higher importance, although the ratio between both processes remains ambiguous. Compared to denitrification, DNRA has been underexplored for the last decades and the key organisms carrying out the process in marine environments are largely unknown. Hence, as a first step to better understand the interplay between denitrification, DNRA and reduction of nitrate to nitrite in estuarine sediments, nitrogen reduction potentials were determined in sediments of the Paulina polder mudflat (Westerschelde estuary. We observed high variability in dominant nitrogen removing processes over a short distance (1.6 m, with nitrous oxide, ammonium and nitrite production rates differing significantly between all sampling sites. Denitrification occurred at all sites, DNRA was either the dominant process (two out of five sites or absent, while nitrate reduction to nitrite was observed in most sites but never dominant. In addition, novel nitrate-to-ammonium reducers assigned to Thalassospira, Celeribacter and Halomonas, for which DNRA was thus far unreported, were isolated, with DNRA phenotype reconfirmed through nrfA gene amplification. This study demonstrates high small scale heterogeneity among dissimilatory nitrate reduction processes in estuarine sediments and provides novel marine DNRA organisms that represent valuable alternatives to the current model organisms.
Dissimilatory nitrogen reduction in intertidal sediments of a temperate estuary: small scale heterogeneity and novel nitrate-to-ammonium reducers.
Decleyre, Helen; Heylen, Kim; Van Colen, Carl; Willems, Anne
The estuarine nitrogen cycle can be substantially altered due to anthropogenic activities resulting in increased amounts of inorganic nitrogen (mainly nitrate). In the past, denitrification was considered to be the main ecosystem process removing reactive nitrogen from the estuarine ecosystem. However, recent reports on the contribution of dissimilatory nitrate reduction to ammonium (DNRA) to nitrogen removal in these systems indicated a similar or higher importance, although the ratio between both processes remains ambiguous. Compared to denitrification, DNRA has been underexplored for the last decades and the key organisms carrying out the process in marine environments are largely unknown. Hence, as a first step to better understand the interplay between denitrification, DNRA and reduction of nitrate to nitrite in estuarine sediments, nitrogen reduction potentials were determined in sediments of the Paulina polder mudflat (Westerschelde estuary). We observed high variability in dominant nitrogen removing processes over a short distance (1.6 m), with nitrous oxide, ammonium and nitrite production rates differing significantly between all sampling sites. Denitrification occurred at all sites, DNRA was either the dominant process (two out of five sites) or absent, while nitrate reduction to nitrite was observed in most sites but never dominant. In addition, novel nitrate-to-ammonium reducers assigned to Thalassospira, Celeribacter, and Halomonas, for which DNRA was thus far unreported, were isolated, with DNRA phenotype reconfirmed through nrfA gene amplification. This study demonstrates high small scale heterogeneity among dissimilatory nitrate reduction processes in estuarine sediments and provides novel marine DNRA organisms that represent valuable alternatives to the current model organisms.
Enhanced Sulfate Reduction and Carbon Sequestration in Sediments Underlying the Core of the Arabian Sea Oxygen Minimum Zone
Fernandes, S. Q.; Mazumdar, A.; Peketi, A.; Bhattacharya, S.; Carvalho, M.; Da Silva, R.; Roy, R.; Mapder, T.; Roy, C.; Banik, S. K.; Ghosh, W.
The oxygen minimum zone (OMZ) of the Arabian Sea in the northern Indian Ocean is one of the three major global sites of open ocean denitrification. The functionally anoxic water column between 150 to 1200 mbsl plays host to unique biogeochemical processes and organism interactions. Little is known, however, about the consequence of the low dissolved oxygen on the underlying sedimentary biogeochemical processes. Here we present, for the first time, a comprehensive investigation of sediment biogeochemistry of the Arabian Sea OMZ by coupling pore fluid analyses with microbial diversity data in eight sediment cores collected across a transect off the west coast of India in the Eastern Arabian Sea. We observed that in sediments underlying the core of the OMZ, high organic carbon sequestration coincides with a high diversity of all bacteria (the majority of which are complex organic matter hydrolyzers) and sulfate reducing bacteria (simple organic compound utilizers). Depth-integrated sulfate reduction rate also intensifies in this territory. These biogeochemical features, together with the detected shallowing of the sulfate-methane interface and buildup of pore-water sulfide, are all reflective of heightened carbon-sulfur cycling in the sediments underlying the OMZ core. Our data suggests that the sediment biogeochemistry of the OMZ is sensitive to minute changes in bottom water dissolved oxygen, and is dictated by the potential abundance and bioavailability of complex to simple carbon compounds which can stimulate a cascade of geomicrobial activities pertaining to the carbon-sulfur cycle. Our findings hold implications in benthic ecology and sediment diagenesis.
Reduction Pathways of Cyclooctatetraene Iron Tricarbonyl as Examined Using Infrared Spectroelectrochemistry.
173/175/179 potentiostat system was used for voltammetric measurements and thin-layer electrolyses . Cyclooctatetraene iron tricarbonyl was synthesised...the subsequent addftion of water . 3 The infrared spectrum for this species contains similar features to those, in Fig. 3B, including a band around 1670
Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts
DEFF Research Database (Denmark)
Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen
is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...
Toxicity of xenobiotics during sulfate, iron, and nitrate reduction in primary sewage sludge suspensions
DEFF Research Database (Denmark)
Elsgaard, Lars
The effect and persistence of six organic xenobiotics was tested under sulfate-, iron-, and nitrate-reducing conditions in primary sewage sludge suspensions. The xenobiotics tested were acenaphthene, phenanthrene, di(2-ethylhexyl)phthalate (DEHP), 4-nonylphenol (4-NP), linear alkylbenzene sulfonate...
Enrichment of Geobacter species in response to stimulation of Fe(III) reduction in sandy aquifer sediments
Snoeyenbos-West, O.L.; Nevin, K.P.; Anderson, R.T.; Lovely, D.R.
Engineered stimulation of Fe(III) has been proposed as a strategy to enhance the immobilization of radioactive and toxic metals in metal-contaminated subsurface environments. Therefore, laboratory and field studies were conducted to determine which microbial populations would respond to stimulation of Fe(III) reduction in the sediments of sandy aquifers. In laboratory studies, the addition of either various organic electron donors or electron shuttle compounds stimulated Fe(III) reduction and resulted in Geobacter sequences becoming important constituents of the Bacterial 16S rDNA sequences that could be detected with PCR amplification and denaturing gradient gel electrophoresis (DGGE). Quantification of Geobacteraceae sequences with a PCR most-probable-number technique indicated that the extent to which numbers of Geobacter increased was related to the degree of stimulation of Fe(III) reduction. Geothrix species were also enriched in some instances, but were orders of magnitude less numerous than Geobacter species. Shewanella species were not detected, even when organic compounds known to be electron donors for Shewanella species were used to stimulate Fe(III) reduction in the sediments. Geobacter species were also enriched in two field experiments in which Fe(III) reduction was stimulated with the addition of benzoate or aromatic hydrocarbons. The apparent growth of Geobacter species concurrent with increased Fe(III) reduction suggests that Geobacter species were responsible for much of the Fe(III) reduction in all of the stimulation approaches evaluated in three geographically distinct aquifers. Therefore, strategies for subsurface remediation that involve enhancing the activity of indigenous Fe(III)-reducing populations in aquifers should consider the physiological properties of Geobacter species in their treatment design.
Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions
Energy Technology Data Exchange (ETDEWEB)
Zhang Fan, E-mail: email@example.com [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Wu Weimin [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Parker, Jack C. [Department of Civil and Environmental Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Mehlhorn, Tonia [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Kelly, Shelly D.; Kemner, Kenneth M. [Biosciences Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Zhang, Gengxin [Key Laboratory of Tibetan Environment Changes and Land Surface Processes, Institute of Tibetan Plateau Research, Chinese Academy of Sciences, P.O. Box 2871, Beijing 100085 (China); Schadt, Christopher; Brooks, Scott C. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Criddle, Craig S. [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States); Watson, David B. [Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Jardine, Philip M. [Biosystems Engineering and Soil Science Department, University of Tennessee, Knoxville, TN 37996 (United States)
Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.
Kinetic analysis and modeling of oleate and ethanol stimulated uranium (VI) bio-reduction in contaminated sediments under sulfate reduction conditions
International Nuclear Information System (INIS)
Zhang Fan; Wu Weimin; Parker, Jack C.; Mehlhorn, Tonia; Kelly, Shelly D.; Kemner, Kenneth M.; Zhang, Gengxin; Schadt, Christopher; Brooks, Scott C.; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.
Microcosm tests with uranium contaminated sediments were performed to explore the feasibility of using oleate as a slow-release electron donor for U(VI) reduction in comparison to ethanol. Oleate degradation proceeded more slowly than ethanol with acetate produced as an intermediate for both electron donors under a range of initial sulfate concentrations. A kinetic microbial reduction model was developed and implemented to describe and compare the reduction of sulfate and U(VI) with oleate or ethanol. The reaction path model considers detailed oleate/ethanol degradation and the production and consumption of intermediates, acetate and hydrogen. Although significant assumptions are made, the model tracked the major trend of sulfate and U(VI) reduction and describes the successive production and consumption of acetate, concurrent with microbial reduction of aqueous sulfate and U(VI) species. The model results imply that the overall rate of U(VI) bioreduction is influenced by both the degradation rate of organic substrates and consumption rate of intermediate products.
Co-existence of Methanogenesis and Sulfate Reduction with Common Substrates in Sulfate-Rich Estuarine Sediments
Directory of Open Access Journals (Sweden)
Michal Sela-Adler
Full Text Available The competition between sulfate reducing bacteria and methanogens over common substrates has been proposed as a critical control for methane production. In this study, we examined the co-existence of methanogenesis and sulfate reduction with shared substrates over a large range of sulfate concentrations and rates of sulfate reduction in estuarine systems, where these processes are the key terminal sink for organic carbon. Incubation experiments were carried out with sediment samples from the sulfate-methane transition zone of the Yarqon (Israel estuary with different substrates and inhibitors along a sulfate concentrations gradient from 1 to 10 mM. The results show that methanogenesis and sulfate reduction can co-exist while the microbes share substrates over the tested range of sulfate concentrations and at sulfate reduction rates up to 680 μmol L-1 day-1. Rates of methanogenesis were two orders of magnitude lower than rates of sulfate reduction in incubations with acetate and lactate, suggesting a higher affinity of sulfate reducing bacteria for the available substrates. The co-existence of both processes was also confirmed by the isotopic signatures of δ34S in the residual sulfate and that of δ13C of methane and dissolved inorganic carbon. Copy numbers of dsrA and mcrA genes supported the dominance of sulfate reduction over methanogenesis, while showing also the ability of methanogens to grow under high sulfate concentration and in the presence of active sulfate reduction.
DOC-dynamics in a small headwater catchment as driven by redox fluctuations and hydrological flow paths – are DOC exports mediated by iron reduction/oxidation cycles?
Directory of Open Access Journals (Sweden)
K.-H. Knorr
Full Text Available Dissolved organic carbon (DOC exports from many catchments in Europe and North-America are steadily increasing. Several studies have sought to explain this observation. As possible causes, a decrease in acid rain or sulfate deposition, concomitant reductions in ionic strength and increasing temperatures were identified. DOC often originates from riparian wetlands; but here, despite higher DOC concentrations, ionic strength in pore waters usually exceeds that in surface waters. In the catchment under study, DOC concentrations were synchronous with dissolved iron concentrations in pore and stream water. This study aims at testing the hypothesis that DOC exports are mediated by iron reduction/oxidation cycles. Following the observed hydrographs, δ18O of water and DOC fluorescence, the wetlands were identified as the main source of DOC. Antecedent biogeochemical conditions, i.e., water table levels in the wetlands, influenced the discharge patterns of nitrate, iron and DOC during an event. The correlation of DOC with pH was positive in pore waters, but negative in surface waters; it was negative for DOC with sulfate in pore waters, but only weak in surface waters. Though, the positive correlation of DOC with iron was universal for pore and surface water. The decline of DOC and iron concentrations in transition from anoxic wetland pore water to oxic stream water suggests a flocculation of DOC with oxidising iron, leading to a drop in pH in the stream during high DOC fluxes. The pore water did not per se differ in pH. There is, thus, a need to consider processes more thoroughly of DOC mobilisation in wetlands when interpreting DOC exports from catchments. The coupling of DOC with iron fluxes suggested that increased DOC exports could at least, in part, be caused by increasing activities in iron reduction, possibly due to increases in temperature, increasing wetness of riparian wetlands, or by a shift from sulfate dominated to iron
An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments. Final report
International Nuclear Information System (INIS)
Pfiffner, Susan
The objective of this research was to examine the importance of microbial community structure in influencing uranium reduction rates in subsurface sediments. If the redox state alone is the key to metal reduction, then any organisms that can utilize the oxygen and nitrate in the subsurface can change the geochemical conditions so metal reduction becomes an energetically favored reaction. Thus, community structure would not be critical in determining rates or extent of metal reduction unless community structure influenced the rate of change in redox. Alternatively, some microbes may directly catalyze metal reduction (e.g., specifically reduce U). In this case the composition of the community may be more important and specific types of electron donors may promote the production of communities that are more adept at U reduction. Our results helped determine if the type of electron donor or the preexisting community is important in the bioremediation of metal-contaminated environments subjected to biostimulation. In a series of experiments at the DOE FRC site in Oak Ridge we have consistently shown that all substrates promoted nitrate reduction, while glucose, ethanol, and acetate always promoted U reduction. Methanol only occasionally promoted extensive U reduction which is possibly due to community heterogeneity. There appeared to be limitations imposed on the community related to some substrates (e.g. methanol and pyruvate). Membrane lipid analyses (phospholipids and respiratory quinones) indicated different communities depending on electron donor used. Terminal restriction fragment length polymorphism and clone libraries indicated distinct differences among communities even in treatments that promoted U reduction. Thus, there was enough metabolic diversity to accommodate many different electron donors resulting in the U bioimmobilization.
Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe0) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and ...
Lactate Oxidation Coupled to Iron or Electrode Reduction by Geobacter sulfurreducens PCA
Call, D. F.
Geobacter sulfurreducens PCA completely oxidized lactate and reduced iron or an electrode, producing pyruvate and acetate intermediates. Compared to the current produced by Shewanella oneidensis MR-1, G. sulfurreducens PCA produced 10-times-higher current levels in lactate-fed microbial electrolysis cells. The kinetic and comparative analyses reported here suggest a prominent role of G. sulfurreducens strains in metaland electrode-reducing communities supplied with lactate. © 2011, American Society for Microbiology.
Lactate Oxidation Coupled to Iron or Electrode Reduction by Geobacter sulfurreducens PCA
Call, D. F.; Logan, B. E.
Geobacter sulfurreducens PCA completely oxidized lactate and reduced iron or an electrode, producing pyruvate and acetate intermediates. Compared to the current produced by Shewanella oneidensis MR-1, G. sulfurreducens PCA produced 10-times-higher current levels in lactate-fed microbial electrolysis cells. The kinetic and comparative analyses reported here suggest a prominent role of G. sulfurreducens strains in metaland electrode-reducing communities supplied with lactate. © 2011, American Society for Microbiology.
Graphic-analytical determination of statics of reduction reextraction of plutonium using iron(2) as a reducing agent
International Nuclear Information System (INIS)
Pochinajlo, A.
The grafic technological scheme of reduction reextraction of plutonium has been designed and the experiments on the laboratory 16-staged extractor of a mixer-settler type have been carried. From the concentration profiles found for a steady stage the content of plutonium(4) and plutonium(3) in organic and water phases in every stage is calculated. Then using the equations of material balance and extraction equilibrium a kinetic formula describing the reduction of plutonium(4) by iron(2f.) in a separate stage is deduced. Since the kinetic parameter A has been found to be close for all the staqes the analytical expression has been obtained with the help of which it is possible to determine a priori the plutonium(4) concentration profile in a reextraction part of the extractor for the given technological process conditions characterized by the defenite A. The plutonium(4) concentration profiles for the organic phase with different values A are presented
Energy Harvesting, Electrode Processes and the Partitioning and Speciation of Solid Phase Iron and Sulfur in Marine Sediments
National Research Council Canada - National Science Library
Reimers, Clare
.... Sediment, pore water and electrode surface analyses indicated that electricity product ion is coupled to the oxidation of dissolved and solid-phase forms of reduced sulfur supplied from the sediments...
Industrial study of iron oxide reduction by injection of carbon particles into the electric arc furnace
International Nuclear Information System (INIS)
Conejo, A. N.; Torres, R.; Cuellar, E.
An industrial study was conducted in electric arc furnaces (EAF) employing 100% direct reduced iron to evaluate the oxidation level of the slag-metal system. Energy consumption is decreased by injecting gaseous oxygen, however, slag oxidation also increases. In order to reduce the extent of oxidation while keeping a high volume of the oxygen injected , it is required: a) to optimize the carbon injection practice, b) to increase the carbon concentration of sponge iron, c) to operate with soluble carbon in both the metal and the slag beyond a critical level and d) to employ a low temperature profile, on average 1,650 degree centigrade. A method to define the proper amount of carbon in sponge iron which considers their metallization as well as the amount of oxygen injected is proposed. The position of the lance is critical in order to optimize the practice of carbon injection and assure a better residence time of the carbon particles within the furnace. (Author) 23 refs
Experimental study and modelling of iron ore reduction by hydrogen; Etude experimentale et modelisation de la reduction du minerai de fer par l'hydrogene
Energy Technology Data Exchange (ETDEWEB)
Wagner, D
In an effort to find new ways to drastically reduce the CO{sub 2} emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterizations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen process. (author)
Reductive Dechlorination of Trichloroethylene and Tetrachloroethylene under Aerobic Conditions in a Sediment Column
Biodegradation of trichloroethylene and tetrachloroethylene under aerobic conditions was studied in a sediment column. Cumulative mass balances indicated 87 and 90% removal for trichloroethylene and tetrachloroethylene, respectively. These studies suggest the potential for simultaneous aerobic and anaerobic biotransformation processes under bulk aerobic conditions.
Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine.
Marmolejo-Rodríguez, Ana Judith; Prego, Ricardo; Meyer-Willerer, Alejandro; Shumilin, Evgueni; Cobelo-García, Antonio
Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Peña Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.
Cave Entrance dependent Spore Dispersion of Filamentous Fungi Isolated from Various Sediments of Iron Ore Cave in Brazil: a colloquy on human threats while caving
Directory of Open Access Journals (Sweden)
Erika Linzi Silva Taylor
Full Text Available Caves are stable environments with characteristics favoring the development of fungi. The fungal community present in a cave also includes pathogenic and opportunistic species out of which some are also served as energy sources in such energy stared ecosystems. Studies on microbial diversity and their role on such energy starved ecosystem are scarce. The present study was aimed to identify the cultivable filamentous fungi present in the various sediment of an iron ore cave and to recognize them as pathogenic and/or opportunistic species. Further the impact of cave entrance on the spore depositions on various distances dependent sediments were analyzed. The results suggest a diverse microbial community inhabiting the cave and an influence of cave entrance over spore deposition on various sediments. We counted a total of 4,549 filamentous fungi that included 34 species of 12 genera: Acremonium, Aspergillus, Cladosporium, Fusarium, Geotrichum, Paecilomyces, Purpureocillium, Penicillium, Torula, Trichoderma, Mucor and Rhizopus. A positive significant relation was observed between spore deposition and distance from cave entrance (p= 0.001. Areas of potential mycoses risks were recognized. This is the first study on microbiological community of an iron ore cave in the country.
Reaction-Based Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center
International Nuclear Information System (INIS)
Yeh, Gour-Tsyh
This research project (started Fall 2004) was funded by a grant to The Pennsylvania State University, University of Central Florida, and The University of Alabama in the Integrative Studies Element of the NABIR Program (DE-FG04-ER63914/63915/63196). Dr. Eric Roden, formerly at The University of Alabama, is now at the University of Wisconsin - Madison. Our project focuses on the development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. This work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and is directly aligned with the Scheibe et al. NABIR FRC Field Project at Area 2
Vivianite Precipitation and Phosphate Sorption following Iron Reduction in Anoxic Soils
DEFF Research Database (Denmark)
Heiberg, Lisa; Bender Koch, Christian; Kjærgaard, Charlotte
, the Fe(II) production reached its maximum and 34% of the citrate–bicarbonate–dithionite extractable Fe (FeCBD) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of FeCBD was reached after 200 d. Neoformation...
Seasonal arsenic accumulation in stream sediments at a groundwater discharge zone.
MacKay, Allison A; Gan, Ping; Yu, Ran; Smets, Barth F
Seasonal changes in arsenic and iron accumulation rates were examined in the sediments of a brook that receives groundwater discharges of arsenic and reduced iron. Clean glass bead columns were deployed in sediments for known periods over the annual hydrologic cycle to monitor changes in arsenic and iron concentrations in bead coatings. The highest accumulation rates occurred during the dry summer period (July-October) when groundwater discharges were likely greatest at the sample locations. The intermediate flow period (October-March), with higher surface water levels, was associated with losses of arsenic and iron from bead column coatings at depths below 2-6 cm. Batch incubations indicated iron releases from solids to be induced by biological reduction of iron (oxy)hydroxide solids. Congruent arsenic releases during incubation were limited by the high arsenic sorption capacity (0.536 mg(As)/mg(Fe)) of unreacted iron oxide solids. The flooded spring (March-June) with high surface water flows showed the lowest arsenic and iron accumulation rates in the sediments. Comparisons of accumulation rates across a shoreline transect were consistent with greater rates at regions exposed above surface water levels for longer times and greater losses at locations submerged below surface water. Iron (oxy)hydroxide solids in the shallowest sediments likely serve as a passive barrier to sorb arsenic released to pore water at depth by biological iron reduction.
Blood transfusion reduction with intravenous iron in gynecologic cancer patients receiving chemotherapy.
Dangsuwan, Penkae; Manchana, Tarinee
To compare the incidence of repeated red blood cell (RBC) transfusion in anemic gynecologic cancer patients receiving platinum-based chemotherapy comparing intravenous and oral iron. Forty-four anemic gynecologic cancer patients (hemoglobin level below 10 mg/dl) who required RBC transfusion were stratified and randomized according to baseline hemoglobin levels and chemotherapy regimen. Study group received 200 mg of intravenous iron sucrose and control group received oral ferrous sulphate 600 mg/day. RBC transfusion requirement in the consecutive cycle of chemotherapy was the primary outcome. Quality of life was evaluated by validated Thai version of the Functional Assessment of Cancer Therapy-Anemia (FACT-An). In a total of the 44 patients, there were 22 patients in each group. Five patients (22.7%) in the study group and 14 patients (63.6%) in the control group required RBC transfusion in consecutive cycle of chemotherapy (p=0.01). No significant difference in baseline hemoglobin and hematocrit levels was demonstrated in both groups. Significantly higher mean hemoglobin and hematocrit levels after treatment were reported in the study group (10.0+/-0.8 g/dl and 30.5+/-2.4%) than the control group (9.5+/-0.9 g/dl and 28.4+/-2.7%). No significant change of total FACT-An scores was noted between before and after treatment in both groups. No serious adverse events were reported and there was no significant difference among adverse events between both groups. Intravenous iron is an alternative treatment for anemic gynecologic cancer patients receiving platinum-based chemotherapy and reduces the incidence of RBC transfusion without serious adverse events.
Graphitic Layer Encapsulated Iron Based Non‐precious Catalysts for the Oxygen Reduction Reaction
DEFF Research Database (Denmark)
Zhong, Lijie
consisting of uniform metallic nanoparticles encapsulated in graphitic layers. The thesis work is conducted aiming at three major objectives: further optimization of the pyrolysis to achieve improved performance of catalysts, investigation of the complex Fe-containing components, and exploration...... of the nitrogen functionalities. Two anions in the electrolyte are used to probe the iron containing active sites towards the ORR, cyanide (CN-) in alkaline and thiocyanate (SCN-) in acidic medium, which seem supporting the above conclusions. These findings provide new insights to the encapsulation structure...
Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine
Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru
Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.
Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration
Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.
Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.
Complete Reductive Dehalogenation of Brominated Biphenyls by Anaerobic Microorganisms in Sediment
Bedard, Donna L.; Van Dort, Heidi M.
We sought to determine whether microorganisms from the polychlorinated biphenyl (PCB)-contaminated sediment in Woods Pond (Lenox, Mass.) could dehalogenate brominated biphenyls. The PCB dechlorination specificities for the microorganisms in this sediment have been well characterized. This allowed us to compare the dehalogenation specificities for brominated biphenyls and chlorinated biphenyls within a single sediment. Anaerobic sediment microcosms were incubated separately at 25°C with 16 different mono- to tetrabrominated biphenyls (350 μM) and disodium malate (10 mM). Samples were extracted and analyzed by gas chromatography with an electron capture detector and a mass spectrometer detector at various times for up to 54 weeks. All of the tested brominated biphenyls were dehalogenated. For most congeners, including 2,6-dibromobiphenyl (26-BB) and 24-25-BB, the dehalogenation began within 1 to 2 weeks. However, for 246-BB and 2-2-BB, debromination was first observed at 7 and 14 weeks, respectively. Most intermediate products did not persist, but when 2-2-BB was produced as a dehalogenation product, it persisted for at least 15 weeks before it was dehalogenated to 2-BB and then to biphenyl. The dehalogenation specificities for brominated and chlorinated biphenyls were similar: meta and para substituents were generally removed first, and ortho substituents were more recalcitrant. However, the brominated biphenyls were better dehalogenation substrates than the chlorinated biphenyls. All of the tested bromobiphenyls, including those with ortho and unflanked meta and para substituents, were ultimately dehalogenated to biphenyl, whereas their chlorinated counterparts either were not dehalogenation substrates or were only partially dehalogenated. Our data suggest that PCB-dechlorinating microorganisms may be able to dehalogenate brominated biphenyls and may exhibit a relaxed specificity for these substrates. PMID:16349530
Novel methodology for the study of mercury methylation and reduction in sediments and water using 197Hg radiotracer
International Nuclear Information System (INIS)
Ribeiro Guevara, Sergio; Perez Catan, Soledad; Zizek, Suzana; Repinc, Urska; Jacimovic, Radojko; Horvat, Milena
Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H 2 SO 4 or HCl were evaluated in freshwater sediments using 197 Hg radiotracer. Values obtained for the 197 Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of 197 Hg 2+ into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg 2+ contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg 2+ contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H 2 SO 4 method is recommended, since it is free from these interferences. 197 Hg radiotracer (T 1/2 = 2.673 d) has a production rate that is about 50 times higher than that of 203 Hg (T 1/2 46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to 203 Hg when it is used it in short-term experiments and produced by the irradiation of 196 Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the 196 Hg isotope is increased, the specific activity of the 197 Hg tracer can be significantly improved. In the present work, 197 Hg tracer was produced from mercury 51.58% enriched in the 196 Hg
Selective separation of iron from uranium in quantitative determination of traces of uranium by alpha spectrometry in soil/sediment sample.
Singhal, R K; Narayanan, Usha; Karpe, Rupali; Kumar, Ajay; Ranade, A; Ramachandran, V
During this work, controlled redox potential methodology was adopted for the complete separation of traces of uranium from the host matrix of mixed hydroxide of Iron. Precipitates of Fe(+2) and Fe(+3) along with other transuranic elements were obtained from acid leached solution of soil by raising the pH to 9 with 14N ammonia solution. The concentration of the uranium observed in the soil samples was 200-600 ppb, whereas in sediment samples, the concentration range was 61-400 ppb.
Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination
Moulin, Solenne; Dentel, Hé lè ne; Pagnoux-Ozherelyeva, Anastassiya; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Lohier, Jean Franç ois; Renaud, Jean Luc
. Festival of amination: Two series of modified Knölker's complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight
Reductive dechlorination of organochlorine pesticides in soils from an abandoned manufacturing facility by zero-valent iron
International Nuclear Information System (INIS)
Cong, Xin; Xue, Nandong; Wang, Shijie; Li, Keji; Li, Fasheng
Several experiments and a model were constructed using conventional granular zero-valent iron (ZVI) particles as the reducing agent to study the reductive dechlorination characteristics of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in soils from a former pesticide-manufacturing site. The results showed that ZVI had good ability for the reductive dechlorination for both HCHs and DDTs. The reductive dechlorination of HCHs and DDTs proceeded at different rates. The pseudo first-order constants of HCHs were greater than those of DDTs. The reductive dechlorination rates in a descending order were γ-HCH > δ-HCH > β-HCH > α-HCH > o,p'-DDT > p,p'-DDT > p,p'-DDE. To discuss the major influential factors over the reductive dechlorination rates of HCHs and DDTs by ZVI, 22 quantum chemical descriptors were computed with the density functional theory at B3LYP/6-31G * level, which characterizes different molecular structures and physicochemical properties of HCHs and DDTs. A polyparameter linear free energy relationship (LFER) model was established, which correlates the reductive dechlorination properties of pollutants with their structural descriptors. Using the partial least squares (PLS) analysis, an optimal two-parameter LFER model was established. q + and q Cl - were more important factors in determining the dechlorination rate of OCPs in the chemical reductive reaction. This optimal model was stable and had good predictability. The model study also showed that the coefficient value of q + was 0.511, which positively correlated with the reductive dechlorination rate constant, whereas q Cl - was negatively correlated with it. The reductive dechlorination rate of pollutants appears to be limited mainly by the rate of dissolution in the aqueous phase. This model can be used to explain the degradation potential of organochlorine pesticides (OCPs) and the trend of residues changing during the soil remediation. Therefore, the study is of
Disturbances to metal partitioning during toxicity testing of iron(II)-rich estuarine pore waters and whole sediments.
Simpson, Stuart L; Batley, Graeme E
Metal partitioning is altered when suboxic estuarine sediments containing Fe(II)-rich pore waters are disturbed during collection, preparation, and toxicity testing. Experiments with model Fe(II)-rich pore waters demonstrated the rates at which adsorptive losses of Cd, Cu, Ni, Mn, Pb, and Zn occur upon exposure to air. Experiments with Zn-contaminated estuarine sediments demonstrated large and often unpredictable changes to metal partitioning during sediment storage, removal of organisms, and homogenization before testing. Small modifications to conditions, such as aeration of overlying waters, caused large changes to the metal partitioning. Disturbances caused by sediment collection required many weeks for reestablishment of equilibrium. Bioturbation by benthic organisms led to oxidation of pore-water Fe(II) and lower Zn fluxes because of the formation of Fe hydroxide precipitates that adsorb pore-water Zn. For five weeks after the addition of organisms to sediments, Zn fluxes increased slowly as the organisms established themselves in the sediments, indicating that the establishment of equilibrium was not rapid. The results are discussed in terms of the dynamic nature of suboxic, Fe(II)-rich estuarine sediments, how organisms perturb their environment, and the importance of understanding chemistry in toxicity testing with whole sediments or pore water. Recommendations are provided for the handling of sediments for toxicity testing.
In Situ UV-Visible Assessment of Iron-Based High-Temperature Water-Gas Shift Catalysts Promoted with Lanthana: An Extent of Reduction Study
Directory of Open Access Journals (Sweden)
Basseem B. Hallac
Full Text Available The extent of reduction of unsupported iron-based high-temperature water-gas shift catalysts with small (<5 wt % lanthana contents was studied using UV-visible spectroscopy. Temperature- programmed reduction measurements showed that lanthana content higher than 0.5 wt % increased the extent of reduction to metallic Fe, while 0.5 wt % of lanthana facilitated the reduction to Fe3O4. In situ measurements on the iron oxide catalysts using mass and UV-visible spectroscopies permitted the quantification of the extent of reduction under temperature-programmed reduction and high-temperature water-gas shift conditions. The oxidation states were successfully calibrated against normalized absorbance spectra of visible light using the Kubelka-Munk theory. The normalized absorbance relative to the fully oxidized Fe2O3 increased as the extent of reduction increased. XANES suggested that the average bulk iron oxidation state during the water-gas shift reaction was Fe+2.57 for the catalyst with no lanthana and Fe+2.54 for the catalysts with 1 wt % lanthana. However, the UV-vis spectra suggest that the surface oxidation state of iron would be Fe+2.31 for the catalyst with 1 wt % lanthana if the oxidation state of iron in the catalyst with 0 wt % lanthana were Fe+2.57. The findings of this paper emphasize the importance of surface sensitive UV-visible spectroscopy for determining the extent of catalyst reduction during operation. The paper highlights the potential to use bench-scale UV-visible spectroscopy to study the surface chemistry of catalysts instead of less-available synchrotron X-ray radiation facilities.
Longevity of granular iron in groundwater treatment processes: solution composition effects on reduction of organohalides and nitroaromatic compounds.
Klausen, Jörg; Vikesland, Peter J; Kohn, Tamar; Burris, David R; Ball, William P; Roberts, A Lynn
Although granular iron permeable reactive barriers (PRBs) are increasingly employed to contain subsurface contaminants, information pertaining to system longevity is sparse. The present investigation redresses this situation by examining the long-term effects of carbonate, silica, chloride, and natural organic matter (NOM) on reactivity of Master Builders iron toward organohalides and nitroaromatic contaminants. Six columns were operated for 1100 days (approximately 4500 pore volumes) and five others for 407 days (approximately 1800 pore volumes). Nine were continuously exposed to mixtures of contaminant species, while the other two were only intermittently exposed in order to differentiate deactivation induced by water (and inorganic cosolutes) from that resulting from contaminant reduction. Contaminants investigated were trichloroethylene, 1,2,3-trichloropropane, 1,1-dichloroethane, 2-nitrotoluene, 4-nitroacetophenone, and 4-nitroanisole. Column reactivity declined substantially over the first 300 days and was dependent on the feed solution chemistry. High carbonate concentrations enhanced reactivity slightly within the first 90 days but produced poorer performance over the long term. Both silica and NOM adversely affected reactivity, while chloride evinced a somewhat mixed effect. Observed contrasts in relative reactivities suggest that trichloroethylene, 1,2,3-trichloropropane, and nitroaromatic compounds all react at different types of reactive sites. Our results indicate that differences in groundwater chemistry should be considered in the PRB design process.
Emerging Energy-efficiency and Carbon Dioxide Emissions-reduction Technologies for the Iron and Steel Industry
Energy Technology Data Exchange (ETDEWEB)
Hasanbeigi, Ali [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Analysis and Environmental Impacts Dept.. China Energy Group; Price, Lynn [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Analysis and Environmental Impacts Dept.. China Energy Group; Arens, Marlene [Fraunhofer Inst. for Systems and Innovation Research (ISI), Karlsruhe (Germany)
Iron and steel manufacturing is among the most energy-intensive industries and accounts for the largest share, approximately 27 percent, of global carbon dioxide (CO2) emissions from the manufacturing sector. The ongoing increase in world steel demand means that this industry's energy use and CO2 emissions continue to grow, so there is significant incentive to develop, commercialize and adopt emerging energy-efficiency and CO2 emissions-reduction technologies for steel production. Although studies from around the world have identified a wide range of energy-efficiency technologies applicable to the steel industry that have already been commercialized, information is limited and/or scattered regarding emerging or advanced energy-efficiency and low-carbon technologies that are not yet commercialized. This report consolidates available information on 56 emerging iron and steel industry technologies, with the intent of providing a well-structured database of information on these technologies for engineers, researchers, investors, steel companies, policy makers, and other interested parties. For each technology included, we provide information on energy savings and environmental and other benefits, costs, and commercialization status; we also identify references for more information.
Effects of ferric iron reduction and regeneration on nitrous oxide and methane emissions in a rice soil.
Huang, Bin; Yu, Kewei; Gambrell, Robert P
A laboratory soil slurry experiment and an outdoor pot experiment were conducted to study effects of ferric iron (Fe(III)) reduction and regeneration on nitrous oxide (N(2)O) and methane (CH(4)) emissions in a rice (Oryza sativa L.) soil. The anoxic slurry experiment showed that enhancing microbial Fe(III) reduction by ferrihydrite amendment (40 mol Fe g(-1)) transitionally stimulated N(2)O production and lowered CH(4) production by 16% during an initial 33-day incubation. Increased regeneration of Fe(III) through a 4-day aeration period in the Fe-amended slurry compared to the control slurry reduced CH(4) emission by 30% in the subsequent 15-day anaerobic incubation. The pot experiment showed that ferrihydrite amendment (63 micromol Fe g(-1)) stimulated N(2)O fluxes in the days following flooding. The Fe amendment suppression on CH(4) emission was obscured in the early season but became significant upon reflooding in the mid- and late-seasons. As a result, seasonal CH(4) emission in Fe-amended pots was 26% lower than the control with a single 2-day drainage and 69% lower with a double 2-day drainage. The reduction in CH(4) emission upon reflooding from the Fe-amended pots was mainly attributed to the increased Fe(III) regeneration during drainage showing a mechanism of Fe(III) regeneration in mitigating CH(4) emission by short-term drainage in flooded soils.
Improved Understanding of Microbial Iron and Sulfate Reduction Through a Combination of Bottom-up and Top-down Functional Proteomics Assays
Energy Technology Data Exchange (ETDEWEB)
Richardson, Ruth [Cornell Univ., Ithaca, NY (United States)
Our overall goal was to improve the understanding of microbial iron and sulfate reduction by evaluating a diverse iron and sulfate reducing organisms utilizing a multi-omics approach combining "top-down" and "bottom-up" omics methodologies. We initiated one of the first combined comparative genomics, shotgun proteomics, RTqPCR, and heterologous expression studies in pursuit of our project objectives. Within the first year of this project, we created a new bioinformatics tool for ortholog identification ("SPOCS"). SPOCS is described in our publication, Curtis et al., 2013. Using this tool we were able to identify conserved orthologous groups across diverse iron and sulfate reducing microorganisms from Firmicutes, gamma-proteobacteria and delta-proteobacteria. For six iron and sulfate reducers we also performed shotgun proteomics ("bottom-up" proteomics including accurate mass and time (AMT) tag and iTRAQ approaches). Cultures include Gram (-) and Gram (+) microbes. Gram (-) were: Geobacter sulfureducens (grown on iron citrate and fumarate), Geobacter bemidjiensis (grown on iron citrate and fumarate), Shewanella oneidiensis (grown on iron citrate and fumarate) and Anaeromyxobacter dehalogenans (grown on iron citrate and fumarate). Although all cultures grew on insoluble iron, the iron precipitates interfered with protein extraction and analysis; which remains a major challenge for researchers in disparate study systems. Among the Gram (-) organisms studied, Anaeromyxobacter dehalogenans remains the most poorly characterized. Yet, it is arguably the most versatile organisms we studied. In this work we have used comparative proteomics to hypothesize which two of the dozens of predicted c-type cytochromes within Anaeromyxobacter dehalogenans may be directly involved in soluble iron reduction. Unfortunately, heterologous expression of these Anaeromyxobacter dehalogenans ctype cytochromes led to poor protein production and/or formation of inclusion bodies
[Reduction of 137caesium contamination in wild boars by supplementing offered food with ammonium-iron-hexa-cyanoferrate].
Morfeld, P; Reddemann, J; Schungel, P; Kienzle, E
This replication study investigated whether the 137caesium (137Cs) contamination of wild boars could be relevantly reduced under field conditions by adding ammonium-iron-hexa-cyanoferrate (AFCF; Prussian blue) to the food. In 285 wild boars that had been shot in six Bavarian hunting territories during the season (November until May) between 01 November 2010 and 10 December 2011 137Cs contamination was analysed. Thirty-five animals originated from two hunting territories in which offered food had been supplemented with 1250 mg AFCF per kilogram food. The control animals showed a mean 137Cs contamination of 522 Bq/kg lean skeletal muscle meat. Direct (univariable) comparisons of the two experimental territories with the four control territories yielded a mean reduction in 137Cs contamination due to Prussian bluefeeding by -211 Bq/kg (p contamination by -380 Bq/kg due to the feeding of Prussian blue in other territories.
Size Control of Iron Oxide Nanoparticles Using Reverse Microemulsion Method: Morphology, Reduction, and Catalytic Activity in CO Hydrogenation
Directory of Open Access Journals (Sweden)
Mohammad Reza Housaindokht
Full Text Available Iron oxide nanoparticles were prepared by microemulsion method and evaluated in Fischer-Tropsch synthesis. The precipitation process was performed in a single-phase microemulsion operating region. Different HLB values of surfactant were prepared by mixing of sodium dodecyl sulfate (SDS and Triton X-100. Transmission electron microscopy (TEM, surface area, pore volume, average pore diameter, pore size distribution, and XRD patterns were used to analyze size distribution, shape, and structure of precipitated hematite nanoparticles. Furthermore, temperature programmed reduction (TPR and catalytic activity in CO hydrogenation were implemented to assess the performance of the samples. It was found that methane and CO2 selectivity and also the syngas conversion increased as the HLB value of surfactant decreased. In addition, the selectivity to heavy hydrocarbons and chain growth probability (α decreased by decreasing the catalyst crystal size.
Effect of repeated pesticide applications on soil properties in cotton fields: I. Impact on microbes, iron reduction capacity and respiration
International Nuclear Information System (INIS)
Vig, K.; Singh, D.K.; Agarwal, H.C.; Dhawan, A.K.; Dureja, P.
Soil microorganisms have a primary catabolic role in the environment through degradation of plant and animal residues. The activities of microorganisms in soil are thus, essential to the global cycling of nutrients. As these pesticides are designed to be biologically active, their continuous use might affect soil microflora either by changing their properties or their numbers, which may lead to impairment in soil fertility. Soil was analyzed for microbial numbers, iron reduction capacity and respiration. Stimulatory, inhibitory or no effects of insecticide treatments were observed on microbes and microbial activities. The insecticides used had only temporary effects on microbes and their activities which disappeared either before the next insecticide treatment was carried out or at the end of experimental period. (author)
Reductive transformations are important processes for determining the fate of organic pollutants in anoxic environments. These processes are most often microbially mediated by both direct and indirect means. For example, specific bacteria transform organic pollutants directly as ...
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts
DEFF Research Database (Denmark)
Hu, Yang; Jensen, Jens Oluf; Zhang, Wei
Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting...
Characterization of the corrinoid iron-sulfur protein tetrachloroethene reductive dehalogenase of Dehalobacter restrictus
Maillard, J.; Schumacher, W.; Vazquez, F.; Regeard, C.; Hagen, W.R.; Holliger, C.
The membrane-bound tetrachloroethene reductive dehalogenase (PCE-RDase) (PceA; EC 184.108.40.206), the terminal component of the respiratory chain of Dehalobacter restrictus, was purified 25-fold to apparent electrophoretic homogeneity. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed a
Sulfate reduction controlled by organic matter availability in deep sediment cores from the saline, alkaline Lake Van (Eastern Anatolia, Turkey
Directory of Open Access Journals (Sweden)
Clemens eGlombitza
Full Text Available As part of the International Continental Drilling Program (ICDP deep lake drilling project PaleoVan, we investigated sulfate reduction (SR in deep sediment cores of the saline, alkaline (salinity 21.4 ‰, alkalinity 155 m mEq-1, pH 9.81 Lake Van, Turkey. The cores were retrieved in the Northern Basin (NB and at Ahlat Ridge (AR and reached a maximum depth of 220 m. Additionally, 65-75 cm long gravity cores were taken at both sites. Sulfate reduction rates (SRR were low (≤ 22 nmol cm-3 d-1 compared to lakes with higher salinity and alkalinity, indicating that salinity and alkalinity are not limiting SR in Lake Van. Both sites differ significantly in rates and depth distribution of SR. In NB, SRR are up to 10 times higher than at AR. Sulfate reduction (SR could be detected down to 19 meters below lake floor (mblf at NB and down to 13 mblf at AR. Although SRR were lower at AR than at NB, organic matter (OM concentrations were higher. In contrast, dissolved OM in the pore water at AR contained more macromolecular OM and less low molecular weight OM. We thus suggest, that OM content alone cannot be used to infer microbial activity at Lake Van but that quality of OM has an important impact as well. These differences suggest that biogeochemical processes in lacustrine sediments are reacting very sensitively to small variations in geological, physical or chemical parameters over relatively short distances.
Microbial reduction of structural iron in interstratified illite-smectite minerals by a sulfate-reducing bacterium.
Liu, D; Dong, H; Bishop, M E; Zhang, J; Wang, H; Xie, S; Wang, S; Huang, L; Eberl, D D
Clay minerals are ubiquitous in soils, sediments, and sedimentary rocks and could coexist with sulfate-reducing bacteria (SRB) in anoxic environments, however, the interactions of clay minerals and SRB are not well understood. The objective of this study was to understand the reduction rate and capacity of structural Fe(III) in dioctahedral clay minerals by a mesophilic SRB, Desulfovibrio vulgaris and the potential role in catalyzing smectite illitization. Bioreduction experiments were performed in batch systems, where four different clay minerals (nontronite NAu-2, mixed-layer illite-smectite RAr-1 and ISCz-1, and illite IMt-1) were exposed to D. vulgaris in a non-growth medium with and without anthraquinone-2,6-disulfonate (AQDS) and sulfate. Our results demonstrated that D. vulgaris was able to reduce structural Fe(III) in these clay minerals, and AQDS enhanced the reduction rate and extent. In the presence of AQDS, sulfate had little effect on Fe(III) bioreduction. In the absence of AQDS, sulfate increased the reduction rate and capacity, suggesting that sulfide produced during sulfate reduction reacted with the phyllosilicate Fe(III). The extent of bioreduction of structural Fe(III) in the clay minerals was positively correlated with the percentage of smectite and mineral surface area of these minerals. X-ray diffraction, and scanning and transmission electron microscopy results confirmed formation of illite after bioreduction. These data collectively showed that D. vulgaris could promote smectite illitization through reduction of structural Fe(III) in clay minerals. © 2011 Blackwell Publishing Ltd.
pH controls over methanogenesis and iron reduction along soil depth profile in Arctic tundra
Zheng, J.; Gu, B.; Wullschleger, S. D.; Graham, D. E.
Increasing soil temperature in the Arctic is expected to accelerate rates of soil organic matter decomposition. However, the magnitude of this impact is uncertain due to the many physical, chemical, and biological processes that control the decomposition pathways. Varying soil redox conditions present a key control over pathways of organic matter decomposition by diverting the flow of reductants among different electron accepting processes and further driving acid-base reactions that alter soil pH. In this study we investigated the pH controls over anaerobic carbon mineralization, methanogenesis, Fe(III) reduction and the interplay between these processes across a range of pH and redox conditions. pH manipulation experiments were conducted by incubating soils representing organic, mineral, cryoturbated transitional layers and permafrost. In the experiments we sought to understand (1) if methanogenesis or Fe(III) reduction had similar pH optima; (2) if this pH response also occurs at `upstream' fermentation process; and (3) if pH alters organo-mineral association or organic matter sorption and desorption and its availability for microbial degradation. Our preliminary results suggest that the common bell-shaped pH response curve provides a good fit for both Fe(III) reduction and methanogenesis, with optimum pH at 6.0-7.0. Exceptions to this were found in transitional layer where methanogenesis rates positively correlated with increasing pH, with maximum rates measured at pH 8.5. It is likely that the transitional layer harbors distinct groups of methanogens that prefer a high pH. Variations in the optimum pH of Fe(III) reduction and methanogenesis may play a significant role in regulating organic matter decomposition pathways and thus greenhouse gas production in thawing soils. These results support biogeochemical modeling efforts to accurately simulate organic matter decomposition under changing redox and pH conditions.
Assessment of air quality in and around a steel industry with direct reduction iron route.
Jena, Pradip K; Behera, Dillip K; Mishra, C S K; Mohanty, Saswat K
The coal based Direct Reduced Iron (DRI) route for secondary steel production is now a preferred choice in India. Steel making is invariably associated with emission of air pollutants into the environment. Air quality monitoring was carried out in Winter, Summer and Rainy seasons of 2008 in eight monitoring stations in the work zone and five stations in the residential zone of an Integrated Steel Industry located in Orissa state, India. Four air quality parameters i.e. SPM, RSPM, SO2 and NO2 were monitored. Mean SPM and RSPM values were found to be significantly high (p < 0.01) at stations nearer to source in both work zone and residential zone .The highest average SPM and RSPM values in the work zone recorded were 4869 microg/m3 and 1420 microg/m3 and in the residential zone 294 microg/m3 and 198 microg/m3 respectively. No significant difference in the SO2 and NO2 levels was observed between the work and residential zones. In general, the values of air pollutants were highest in Winter followed by Summer and Rainy season. SPM and RSPM values exceeded the National Air Quality Standards (NAAQS) in both the residential and work zones.
Novel methodology for the study of mercury methylation and reduction in sediments and water using 197Hg radiotracer.
Ribeiro Guevara, Sergio; Zizek, Suzana; Repinc, Urska; Pérez Catán, Soledad; Jaćimović, Radojko; Horvat, Milena
Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H2SO4 or HCl were evaluated in freshwater sediments using 197Hg radiotracer. Values obtained for the 197Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of 197Hg2+ into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg2+ contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg2+ contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H2SO4 method is recommended, since it is free from these interferences. 197Hg radiotracer (T1/2=2.673 d) has a production rate that is about 50 times higher than that of 203Hg (T1/2=46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to 203Hg when it is used it in short-term experiments and produced by the irradiation of 196Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the 196Hg isotope is increased, the specific activity of the 197Hg tracer can be significantly improved. In the present work, 197Hg tracer was produced from mercury 51.58% enriched in the 196Hg isotope, and a 340-fold
Thermophilic Sulfate Reduction in Hydrothermal Sediment of Lake Tanganyika, East-Africa
DEFF Research Database (Denmark)
at up to 70 and 75 degrees C, with optima at 63 and 71 degrees C, respectively. Several sporulating thermophilic enrichments were morphologically similar to Desulfotomaculum spp. Dissimilatory sulfate reduction in the studied hydrothermal area of Lake Tanganyika apparently has an upper temperature limit...
High-resolution imaging of labile phosphorus and its relationship with iron redox state in lake sediments
DEFF Research Database (Denmark)
Gao, Yulu; Liang, Tao; Tian, Shuhan
a regional summer algal bloom. Two-dimensional distributions of labile P in sediments were imaged with the Zr-Oxide DGT without destruction of the original structure of the sediment layer at four sites of the lake. The concentration of DGT-labile P in the sediments, ranging from 0.007 to 0.206 mg L(-1......), was highly heterogeneous across the profiles. The values of apparent diffusion flux (Fd) and release flux (Fr) of P varied between -0.027-0.197 mg m(-2) d(-1) and 0.037-0.332 mg m(-2) d(-1), respectively. Labile P showed a high and positive correlation (p
Speciation of chromium, copper, iron, manganese, nickel, and zinc of sediment from the Densu River by sequential extraction
International Nuclear Information System (INIS)
Carboo, D.; Brimah, A.K.; Debrah, C.
Total concentrations of the broad metal spectrum and speciation of Cr, Cu, Fe, Ni, Mn and Zn in sediments of River Densu are studied in order to establish the extent of pollution and their capacity of remobilization. Eight composite samples were analyzed, major components of the sediments were studied using Instrumental Neutron Activation Analysis (INAA) and Atomic Absorption Spectrophotometer (AAS). From the results obtained, it can be concluded that the sediment has Cd value above the normal range. The distribution of the elements in various fractions depends largely on the element. Most of the elements have the bulk of their concentration in the residual fraction. (author)
Alteration in Solid State Phosphorous With Depth in Sediments Along the Salinity Transition Zone of a Major Chesapeake Bay Tributary
Hartzell, J. L.; Jordan, T. E.
Determining the fate of particulate phosphorus in estuaries is essential for addressing the widespread problem of estuarine eutrophication, and is key to understanding P cycling and developing accurate global P budgets. Prominent reservoirs of P in surficial sediments include particulate P associated with iron or organic C. However, the importance of these reservoirs changes with the decomposition of organic matter and the reduction of iron. Also, the importance of iron bound P may decrease with increasing salinity due to the formation of iron sulfides. To investigate estuarine P burial and its relationship to salinity, we collected sediment cores of one-meter depth along the salinity gradient of the Patuxent River estuary (Maryland, USA), a major tributary of Chesapeake Bay. The sediments were analyzed using a sequential sedimentary extraction procedure that quantifies five separate reservoirs of particulate P. Total phosphorus concentrations in freshwater sediments were significantly higher than those in more saline sediments at all depths. Conversely, porewater phosphate concentrations were significantly lower in freshwater sediments than in the more saline sediments. Total P in the saline sediment cores decreased with depth, correlating to a reduction in iron-bound P. However, we did not find a concurrent increase in authigenic apatite with depth. Our findings indicate that mechanisms controlling changes in P sorption to sediments change profoundly with salinity and may contribute to increased bioavailability of phosphates with increasing salinity.
Reduction of 137caesium contamination in wild boars by supplementing offered food with ammonium-iron-hexa-cyanoferrate
International Nuclear Information System (INIS)
Morfeld, P.; Kienzle, E.
This replication study investigated whether the 137 caesium ( 137 Cs) contamination of wild boars could be relevantly reduced under field conditions by adding ammonium-iron-hexa-cyanoferrate (AFCF; Prussian blue) to the food. In 285 wild boars that had been shot in six Bavarian hunting territories during the season (November until May) between 01 November 2010 and 10 December 2011 137 Cs contamination was analysed. Thirty-five animals originated from two hunting territories in which offered food had been supplemented with 1250 mg AFCF per kilogram food. The control animals showed a mean 137 Cs contamination of 522 Bq/kg lean skeletal muscle meat. Direct (univariable) comparisons of the two experimental territories with the four control territories yielded a mean reduction in 137 Cs contamination due to Prussian bluefeeding by -211 Bq/kg (p < 0.001). Multivariable mo dels that took potential confounders into account (age, weight, sex, hunting date, territory) estimated the effect to be -344 Bq/kg (p < 0.05). This replication study confirmed the finding of Kienzle et al. (12) who described a statistically significant reduction in 137 Cs contamination by -380 Bq/kg due to the feeding of Prussian blue in other territories. [de
Flavins secreted by roots of iron-deficient Beta vulgaris enable mining of ferric oxide via reductive mechanisms.
Sisó-Terraza, Patricia; Rios, Juan J; Abadía, Javier; Abadía, Anunciación; Álvarez-Fernández, Ana
Iron (Fe) is abundant in soils but generally poorly soluble. Plants, with the exception of Graminaceae, take up Fe using an Fe(III)-chelate reductase coupled to an Fe(II) transporter. Whether or not nongraminaceous species can convert scarcely soluble Fe(III) forms into soluble Fe forms has deserved little attention so far. We have used Beta vulgaris, one among the many species whose roots secrete flavins upon Fe deficiency, to study whether or not flavins are involved in Fe acquisition. Flavins secreted by Fe-deficient plants were removed from the nutrient solution, and plants were compared with Fe-sufficient plants and Fe-deficient plants without flavin removal. Solubilization of a scarcely soluble Fe(III)-oxide was assessed in the presence or absence of flavins, NADH (nicotinamide adenine dinucleotide, reduced form) or plant roots, and an Fe(II) trapping agent. The removal of flavins from the nutrient solution aggravated the Fe deficiency-induced leaf chlorosis. Flavins were able to dissolve an Fe(III)-oxide in the presence of NADH. The addition of extracellular flavins enabled roots of Fe-deficient plants to reductively dissolve an Fe(III)-oxide. We concluded that root-secretion of flavins improves Fe nutrition in B. vulgaris. Flavins allow B. vulgaris roots to mine Fe from Fe(III)-oxides via reductive mechanisms. © 2015 CSIC New Phytologist © 2015 New Phytologist Trust.
Scenario analysis on CO2 emissions reduction potential in China's iron and steel industry
International Nuclear Information System (INIS)
Wang Ke; Wang Can; Lu Xuedu; Chen Jining
The international climate community has begun to assess a range of possible options for strengthening the international climate change effort after 2012. Analysis of the potential for sector-based emissions reduction and relevant mitigation options will provide the necessary background information for the debate. In order to assess the CO 2 abatement potential of China's steel industry, a model was developed using LEAP software to generate 3 different CO 2 emission scenarios for the industry from 2000 to 2030. The abatement potentials of different scenarios were compared, and their respective feasibilities were assessed according to the cost information. High priority abatement measures were then identified. The results show that the average CO 2 abatement per year in the Recent Policy scenario and in the New Policy scenario, compared with the reference scenario, are 51 and 107 million tons, respectively. The corresponding total incremental costs are 9.34 and 80.95 billion dollars. It is concluded that there is great potential for CO 2 abatement in China's steel industry. Adjusting the structure of the industry and technological advancement will play an important role in emissions reduction. Successful implementation of current sustainable development policies and measures will result in CO 2 abatement at a low cost. However, to achieve higher levels of abatement, the cost will increase dramatically. In the near future, specific energy conservation technologies such as dry coke quenching, exhaust gas and heat recovery equipment will be of great significance. However, taking a long term perspective, emissions reduction will rely more on the adjustment of production processes and the application of more modern large scale plants. Advanced blast furnace technology will inevitably play an important role
Reduction of neptunium(V) and uranium(VI) in bicarbonate solutions by iron(II)
International Nuclear Information System (INIS)
Gogolev, A.V.; Zakharova, E.V.; Rodygina, N.I.; Fedoseev, A.M.; Shilov, V.P.
Interaction of Np(VI) and Fe(II) compounds in bicarbonate solutions is investigated. Interaction of Np(V) with Fe(II) in the presence of phthalate-ions is studied briefly. Fe(II) compounds reduce Np(V) compounds in saturated with Ar or CO 2 solutions with any bicarbonate-ion concentrations. Chemical reaction kinetics is studied. Reduction of U(VI) by Fe(II) compounds takes place in the case of diluted bicarbonate solutions. UO 2 and FeOOH are products of reaction at raised temperatures [ru
Temperature dependence of microbial degradation of organic matter in marine sediments: polysaccharide hydrolysis, oxygen consumption, and sulfate reduction
DEFF Research Database (Denmark)
Arnosti, C.; Jørgensen, BB; Sagemann, J.
The temperature dependence of representative initial and terminal steps of organic carbon remineralization was measured at 2 temperate sites with annual temperature ranges of 0 to 30 degrees C and 4 to 15 degrees C and 2 Arctic sites with temperatures of 2.6 and -1.7 degrees C. Slurried sediments...... were incubated in a temperature gradient block spanning a temperature range of ca 45 degrees C. The initial step of organic carbon remineralization, macromolecule hydrolysis, was measured via the enzymatic hydrolysis of fluorescently labeled polysaccharides. The terminal steps of organic carbon...... remineralization were monitored through consumption of oxygen and reduction of (SO42-)-S-35. At each of the 4 sites, the temperature response of the initial step of organic carbon remineralization was similar to that of the terminal steps. Although optimum temperatures were always well above ambient environmental...
Synthesis of high intrinsic loss power aqueous ferrofluids of iron oxide nanoparticles by citric acid-assisted hydrothermal-reduction route
International Nuclear Information System (INIS)
Behdadfar, Behshid; Kermanpur, Ahmad; Sadeghi-Aliabadi, Hojjat; Morales, Maria del Puerto; Mozaffari, Morteza
Monodispersed aqueous ferrofluids of iron oxide nanoparticle were synthesized by hydrothermal-reduction route. They were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy and dynamic light scattering. The results showed that certain concentrations of citric acid (CA) are required to obtain only magnetic iron oxides with mean particle sizes around 8 nm. CA acts as a modulator and reducing agent in iron oxide formation which controls nanoparticle size. The XRD, magnetic and heating measurements showed that the temperature and time of hydrothermal reaction can affect the magnetic properties of obtained ferrofluids. The synthesized ferrofluids were stable at pH 7. Their mean hydrodynamic size was around 80 nm with polydispersity index (PDI) of 0.158. The calculated intrinsic loss power (ILP) was 9.4 nHm 2 /kg. So this clean and cheap route is an efficient way to synthesize high ILP aqueous ferrofluids applicable in magnetic hyperthermia. - Graphical abstract: Monodispersed aqueous ferrofluids of iron oxide nanoparticles were synthesized by hydrothermal-reduction method with citric acid as reductant which is an efficient way to synthesize aqueous ferrofluids applicable in magnetic hyperthermia. Highlights: ► Aqueous iron oxide ferrofluids were synthesized by hydrothermal-reduction route. ► Citric acid acted as reducing agent and surfactant in the route. ► This is a facile, low energy and environmental friendly route. ► The aqueous iron oxide ferrofluids were monodispersed and stable at pH of 7. ► The calculated intrinsic loss power of the synthesized ferrofluids was very high.
57Fe-Mössbauer spectroscopy and electrochemical activities of graphitic layer encapsulated iron electrocatalysts for the oxygen reduction reaction
DEFF Research Database (Denmark)
Zhong, Lijie; Frandsen, Cathrine; Mørup, Steen
Graphitic layer encapsulated iron based nanoparticles (G@FeNPs) have recently been disclosed as an interesting type of highly active electrocatalysts for the oxygen reduction reaction (ORR). However, the complex composition of the metal-containing components and their contributions in catalysis r...
Kinetics of nitrate adsorption and reduction by nano-scale zero valent iron (NZVI): Effect of ionic strength and initial pH
DEFF Research Database (Denmark)
Kim, Do-Gun; Hwang, Yuhoon; Shin, Hang-Sik
Kinetic models for pollutants reduction by Nano-scale Zero Valent Iron (NZVI) were tested in this study to gain a better understanding and description of the reaction. Adsorption kinetic models and a heterogeneous catalytic reaction kinetic equation were proposed for nitrate removal and for ammon...
Benthic iron and phosphorus release from river dominated shelf sediments under varying bottom water O2 concentrations.
Ghaisas, N. A.; Maiti, K.; White, J. R.
Phosphorus (P) cycling in coastal ocean is predominantly controlled by river discharge and biogeochemistry of the sediments. In coastal Louisiana, sediment biogeochemistry is strongly influenced by seasonally fluctuating bottom water O2, which, in turn transitions the shelf sediments from being a sink to source of P. Sediment P-fluxes were 9.73 ± 0.76 mg / m2 /d and 0.67±0.16 mg/m2/d under anaerobic and aerobic conditions respectively, indicating a 14 times higher P-efflux from oxygen deprived sediments. A high sedimentary oxygen consumption rate of 889 ± 33.6 mg/m2/d was due to organic matter re-mineralization and resulted in progressively decreasing the water column dissolved O2 , coincident with a P-flux of 7.2 ± 5.5 mg/m2/d from the sediment. Corresponding water column flux of Fe total was 19.7 ± 7.80 mg/m2/d and the sediment-TP decreased from 545 mg/Kg to 513 mg/Kg. A simultaneous increase in pore water Fe and P concentrations in tandem with a 34.6% loss in sedimentary Fe-bound P underscores the importance of O2 on coupled Fe- P biogeochemistry. This study suggests that from a 14,025 sq. km hypoxia area, Louisiana shelf sediments can supply 1.33x105 kg P/day into the water column compared to 0.094 x 105 kg P/day during the fully aerobic water column conditions.
Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron
Energy Technology Data Exchange (ETDEWEB)
Sun, Yubing [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Ding, Congcong; Cheng, Wencai [Institute of Plasma Physics, Chinese Academy of Science, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke, E-mail: firstname.lastname@example.com [School of Environment and Chemical Engineering, North China Electric Power University, Beijing 102206 (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)
Graphical abstract: - Highlights: • Sorption and in-situ reduction of U(VI) is observed. • The composites are more effective for U(VI) removal and solidification. • The inner-sphere surface complexes are observed. - Abstract: The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH{sup −} groups of rGO and the massive enrichment of Fe{sup 2+} on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the U-C (at ∼2.9 Å) and U-Fe (at ∼3.2 Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management.
Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction
Energy Technology Data Exchange (ETDEWEB)
Zhang, Jie; Chen, Jinwei, E-mail: email@example.com; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin, E-mail: firstname.lastname@example.com
Graphical abstract: A hybrid catalyst was prepared via a quite green and simple method to achieve an one-pot synthesis of the N-doping carbon, tungsten carbides, and iron/cobalt carbides. It exhibited comparable electrocatalytic activity, higher durability and ability to methanol tolerance compared with commercial Pt/C to ORR. - Highlights: • A novel type of hybrid Fe/Co/WC@NC catalysts have been successfully synthesized. • The hybrid catalyst also exhibited better durability and methanol tolerance. • Multiple effective active sites of Fe{sub 3}C, Co{sub 3}C, WC, and NC help to improve catalytic performance. - Abstract: This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe{sub 3}C and Co{sub 3}C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe{sub 3}C, and Co{sub 3}C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.
Effects of thiamphenicol on nitrate reduction and N2O release in estuarine and coastal sediments
International Nuclear Information System (INIS)
Yin, Guoyu; Hou, Lijun; Liu, Min; Zheng, Yanling; Li, Xiaofei; Lin, Xianbiao; Gao, Juan; Jiang, Xiaofen
Nitrate overload is an important driver of water pollution in most estuarine and coastal ecosystems, and thus nitrate reduction processes have attracted considerable attention. Antibiotics contamination is also an emerging environmental problem in estuarine and coastal regions as a result of growing production and usage of antibiotics. However, the effects of antibiotics on nitrate reduction remain unclear in these aquatic ecosystems. In this study, continuous-flow experiments were conducted to examine the effects of thiamphenicol (TAP, a common chloramphenicol antibiotic) on nitrate reduction and greenhouse gas N 2 O release. Functional genes involved in nitrogen transformation were also quantified to explore the microbial mechanisms of the TAP influence. Production of N 2 were observed to be inhibited by TAP treatment, which implied the inhibition effect of TAP on nitrate reduction processes. As intermediate products of nitrogen transformation processes, nitrite and N 2 O were observed to accumulate during the incubation. Different TAP inhibition effects on related functional genes may be the microbial mechanism for the changes of nutrient fluxes, N 2 fluxes and N 2 O release rates. These results indicate that the antibiotics residues in estuarine and coastal ecosystems may contribute to nitrate retention and N 2 O release, which could be a major factor responsible for eutrophication and greenhouse effects. - Highlights: • Production of N 2 are inhibited by the TAP treatment. • Accumulation of nitrite and N 2 O is stimulated by TAP treatment. • Different TAP effects on functional genes may be the microbial mechanism. - TAP inhibits the production of N 2 and stimulates the accumulation of nitrite and N 2 O due to its different inhibition effects on functional genes.
An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments
International Nuclear Information System (INIS)
Pfiffner, Susan M.; Brandt, Craig C.; Kostka, Joel E.; Palumbo, Anthony V.
Our current research represents a joint effort between Oak Ridge National Laboratory (ORNL), Florida State University (FSU), and the University of Tennessee. ORNL will serve as the lead institution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliverables. This project was initiated in November, 2004, in the Integrative Studies Element of the NABIR program. The overall goal of our project is to provide an improved understanding of the relationships between microbial community structure, geochemistry, and metal reduction rates. The research seeks to address the following questions: Is the metabolic diversity of the in situ microbial community sufficiently large and redundant that bioimmobilization of uranium will occur regardless of the type of electron donor added to the system? Are their donor specific effects that lead to enrichment of specific community members that then impose limits on the functional capabilities of the system? Will addition of humics change rates of uranium reduction without changing community structure? Can resource-ratio theory be used to understand changes in uranium reduction rates and community structure with respect to changing C:P ratios?
An Integrated Assessment of Geochemical and Community Structure Determinants of Metal Reduction Rates in Subsurface Sediments
International Nuclear Information System (INIS)
Kostka, Joel E.
This project represented a joint effort between Oak Ridge National Laboratory (ORNL), the University of Tennessee (UT), and Florida State University (FSU). ORNL served as the lead in-stitution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliver-ables. In situ uranium bioremediation is focused on biostimulating indigenous microorganisms through a combination of pH neutralization and the addition of large amounts of electron donor. Successful biostimulation of U(VI) reduction has been demonstrated in the field and in the laboratory. However, little data is available on the dynamics of microbial populations capable of U(VI) reduction, and the differences in the microbial community dynamics between proposed electron donors have not been explored. In order to elucidate the potential mechanisms of U(VI) reduction for optimization of bioremediation strategies, structure-function relationships of microbial populations were investigated in microcosms of subsurface materials cocontaminated with radionuclides and nitrate from the Oak Ridge Field Research Center (ORFRC), Oak Ridge, Tennessee.
Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells
Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang
Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.
Novel methodology for the study of mercury methylation and reduction in sediments and water using {sup 197}Hg radiotracer
Energy Technology Data Exchange (ETDEWEB)
Ribeiro Guevara, Sergio; Perez Catan, Soledad [Centro Atomico Bariloche, Laboratorio de Analisis por Activacion Neutronica, Bariloche (Argentina); Zizek, Suzana; Repinc, Urska; Jacimovic, Radojko; Horvat, Milena [Jozef Stefan Institute, Department of Environmental Sciences, Ljubljana (Slovenia)
Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H{sub 2}SO{sub 4} or HCl were evaluated in freshwater sediments using {sup 197}Hg radiotracer. Values obtained for the {sup 197}Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of {sup 197}Hg{sup 2+} into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg{sup 2+} contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg{sup 2+} contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H{sub 2}SO{sub 4} method is recommended, since it is free from these interferences. {sup 197}Hg radiotracer (T{sub 1/2} = 2.673 d) has a production rate that is about 50 times higher than that of {sup 203}Hg (T{sub 1/2} = 46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to {sup 203}Hg when it is used it in short-term experiments and produced by the irradiation of {sup 196}Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the {sup 196}Hg isotope is increased, the specific activity of the {sup 197}Hg tracer can be significantly improved. In
Bromate Reduction by Iron(II during Managed Aquifer Recharge: A Laboratory-Scale Study
Directory of Open Access Journals (Sweden)
Feifei Wang
Full Text Available The removal of bromate (BrO3− as a byproduct of ozonation in subsequent managed aquifer recharge (MAR systems has so far gained little attention. This preliminary study with anoxic batch experiments was executed to explore the feasibility of chemical BrO3− reduction in Fe-reducing zones of MAR systems and to estimate potential inhibition by NO3−. Results show that the reaction rate was affected by initial Fe2+/BrO3− ratios and by pH. The pH dropped significantly due to the hydrolysis of Fe3+ to hydrous ferric oxide (HFO flocs. These HFO flocs were found to adsorb Fe2+, especially at high Fe2+/BrO3− ratios, whereas at low Fe2+/BrO3− ratios, the mass sum loss of BrO3− and Br− indicated intermediate species formation. Under MAR conditions with relatively low BrO3− and Fe2+ concentrations, BrO3− can be reduced by naturally occurring Fe2+, as the extensive retention time in MAR systems will compensate for the slow reaction kinetics of low BrO3− and Fe2+ concentrations. Under specific flow conditions, Fe2+ and NO3− may co-occur during MAR, but NO3− hardly competes with BrO3−, since Fe2+ prefers BrO3− over NO3−. However, it was found that when NO3− concentration exceeds BrO3− concentration by multiple orders of magnitude, NO3− may slightly inhibit BrO3− reduction by Fe2+.
Greek "red mud" residue: A study of microwave reductive roasting followed by magnetic separation for a metallic iron recovery process
Energy Technology Data Exchange (ETDEWEB)
Samouhos, Michail, E-mail: firstname.lastname@example.com [School of Mining and Metallurgical Engineering, Laboratory of Metallurgy, National Technical University of Athens, 9, Iroon Polytechniou Street, 157 80 Zografou, Athens (Greece); Taxiarchou, Maria; Tsakiridis, Petros E. [School of Mining and Metallurgical Engineering, Laboratory of Metallurgy, National Technical University of Athens, 9, Iroon Polytechniou Street, 157 80 Zografou, Athens (Greece); Potiriadis, Konstantinos [Greek Atomic Energy Commission (GAEC), Patriarxou Grigoriou and Neapoleos, P.O. Box 60092, 15310 Agia Paraskevi, Athens (Greece)
Highlights: • Microwave reduction of a red mud. •Measurement of real and imaginary permittivity of red mud–lignite mixture. •Red mud was subjected to reductive roasting and magnetic separation processes. •The optimum concentrate contains 31.6% iron with a 69.3% metallization degree. •{sup 226}Ra, {sup 228}Ra, {sup 238}U, {sup 228}Th, {sup 232}Th, {sup 40}K were detected in the magnetic concentrate. -- Abstract: The present research work is focused on the development of an alternative microwave reductive roasting process of red mud using lignite (30.15 wt.% C{sub fix}), followed by wet magnetic separation, in order to produce a raw material suitable for sponge or cast iron production. The reduction degree of iron was controlled by both the reductive agent content and the microwave heating time. The reduction followed the Fe{sub 2}O{sub 3} → Fe{sub 3}O{sub 4} → FeO → Fe sequence. The dielectric constants [real (ε′) and imaginary (ε″) permittivities] of red mud–lignite mixture were determined at 2.45 GHz, in the temperature range of 25–1100 °C. The effect of parameters such as temperature, intensity of reducing conditions, intensity of magnetic field and dispersing agent addition rate on the result of both processes was investigated. The phase's transformations in reduction process with microwave heating were determined by X-ray diffraction analysis (XRD) in combination with thermogravimetric/differential thermal analysis (TGA/DTA). The microstructural and morphological characterization of the produced calcines was carried out by scanning electron microscopy (SEM). At the optimum conditions a magnetic concentrate with total iron concentration of 35.15 and 69.3 wt.% metallization degree was obtained.
Biot's coefficient as an indicator of strength and porosity reduction: Calcareous sediments from Kerguelen Plateau
DEFF Research Database (Denmark)
Alam, Mohammad Monzurul; Borre, Mai Kirstine; Fabricius, Ida Lykke
β to fall, even when porosity remains constant. Biot's coefficient correlates with strength-indicating properties: compressional and shear modulus, oedometer modulus, yield strength, strain from direct loading and creep strain. Our data indicate that β may be used for predicting the diagenetic...... Biot's coefficient, β. In calcareous ooze, β is one. Mechanical compaction reduces porosity, but only leads to a minor decrease in β. Recrystallization renders particles smoother, but does not lead to reduction in β unless it gives rise to pore stiffening cementation. Pore stiffening cementation causes...
High strength, biodegradable and cytocompatible alpha tricalcium phosphate-iron composites for temporal reduction of bone fractures.
Montufar, E B; Casas-Luna, M; Horynová, M; Tkachenko, S; Fohlerová, Z; Diaz-de-la-Torre, S; Dvořák, K; Čelko, L; Kaiser, J
In this work alpha tricalcium phosphate (α-TCP)/iron (Fe) composites were developed as a new family of biodegradable, load-bearing and cytocompatible materials. The composites with composition from pure ceramic to pure metallic samples were consolidated by pulsed electric current assisted sintering to minimise processing time and temperature while improving their mechanical performance. The mechanical strength of the composites was increased and controlled with the Fe content, passing from brittle to ductile failure. In particular, the addition of 25 vol% of Fe produced a ceramic matrix composite with elastic modulus much closer to cortical bone than that of titanium or biodegradable magnesium alloys and specific compressive strength above that of stainless steel, chromium-cobalt alloys and pure titanium, currently used in clinic for internal fracture fixation. All the composites studied exhibited higher degradation rate than their individual components, presenting values around 200 μm/year, but also their compressive strength did not show a significant reduction in the period required for bone fracture consolidation. Composites showed preferential degradation of α-TCP areas rather than β-TCP areas, suggesting that α-TCP can produce composites with higher degradation rate. The composites were cytocompatible both in indirect and direct contact with bone cells. Osteoblast-like cells attached and spread on the surface of the composites, presenting proliferation rate similar to cells on tissue culture-grade polystyrene and they showed alkaline phosphatase activity. Therefore, this new family of composites is a potential alternative to produce implants for temporal reduction of bone fractures. Biodegradable alpha-tricalcium phosphate/iron (α-TCP/Fe) composites are promising candidates for the fabrication of temporal osteosynthesis devices. Similar to biodegradable metals, these composites can avoid implant removal after bone fracture healing, particularly in
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
Energy Technology Data Exchange (ETDEWEB)
Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu; Feng, Zhenxing; Karakalos, Stavros; Luo, Langli; Qiao, Zhi; Xie, Xiaohong; Wang, Chongmin; Su, Dong; Shao, Yuyan; Wu, Gang (BNL); (Oregon State U.); (SC); (PNNL); (Buffalo)
It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability
Impact of estuarine gradients on reductive dechlorination of 1,2,3,4-tetrachlorodibenzo-p-dioxin in river sediment enrichment cultures.
Dam, Hang T; Häggblom, Max M
Polychlorinated dibenzo-p-dioxins (PCDDs) are among the most persistent organic pollutants. Although the total input of PCDDs into the environment has decreased substantially over the past four decades, their input via non-point sources is still increasing, especially in estuarine metropolitan areas. Here we report on the microbially mediated reductive dechlorination of PCDDs in anaerobic enrichment cultures established from sediments collected from five locations along the Hackensack River, NJ and investigate the impacts of sediment physicochemical characteristics on dechlorination activity. Dechlorination of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TeCDD) and abundance of Dehalococcoides spp. negatively correlated with salinity and sulfate concentration in sediments used to establish the cultures. 1,2,3,4-TeCDD was dechlorinated to a lesser extent in cultures established from sediments from the tidally influenced estuarine mouth of the river. In cultures established from low salinity sediments, 1,2,3,4-TeCDD was reductively dechlorinated with the accumulation of 2-monochlorodibenzo-p-dioxin as the major product. Sulfate concentrations above 2 mM inhibited 1,2,3,4-TecDD dechlorination activity. Consecutive lateral- and peri- dechlorination took place in enrichment cultures with a minimal accumulation of 2,3-dichlorodibenzo-p-dioxin in active cultures. A Dehalococcoides spp. community was enriched and accounted for up to 64% of Chloroflexi detected in these sediment cultures. Copyright © 2016 Elsevier Ltd. All rights reserved.
Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center, Subproject to Co-PI Eric E. Roden. Final Report
International Nuclear Information System (INIS)
Roden, Eric E.
This report summarizes research conducted in conjunction with a project entitled 'Reaction-Based Reactive Transport Modeling of Iron Reduction and Uranium Immobilization at Area 2 of the NABIR Field Research Center', which was funded through the Integrative Studies Element of the former NABIR Program (now the Environmental Remediation Sciences Program) within the Office of Biological and Environmental Research. Dr. William Burgos (The Pennsylvania State University) was the overall PI/PD for the project, which included Brian Dempsey (Penn State), Gour-Tsyh (George) Yeh (Central Florida University), and Eric Roden (formerly at The University of Alabama, now at the University of Wisconsin) as separately-funded co-PIs. The project focused on development of a mechanistic understanding and quantitative models of coupled Fe(III)/U(VI) reduction in FRC Area 2 sediments. The work builds on our previous studies of microbial Fe(III) and U(VI) reduction, and was directly aligned with the Scheibe et al. ORNL FRC Field Project at Area 2.
Ordered hierarchically porous carbon codoped with iron and nitrogen as electrocatalyst for the oxygen reduction reaction.
Deng, Chengwei; Zhong, Hexiang; Yao, Lan; Liu, Sisi; Xu, Zhuang; Zhang, Huamin
N-doped carbon catalysts have attracted great attention as potential alternatives to expensive Pt-based catalysts used in fuel cells. Herein, an ordered hierarchically porous carbon codoped with N and Fe (Fe-NOHPC) is prepared by an evaporation-induced self-assembly process followed by carbonization under ammonia. The soft template and Fe species promote the formation of the porous structure and facilitate the oxygen reduction reaction (ORR).The catalyst possesses an ordered hierarchically porous structure with a large surface area (1172.5 m(2) g(-1) ) and pore volume of 1.03 cm(3) g(-1) . Compared to commercial 20% Pt/C, it exhibits better ORR catalytic activity and higher stability as well as higher methanol tolerance in an alkaline electrolyte, which demonstrates its potential use in fuel cells as a nonprecious cathode catalyst. The N configuration, Fe species, and pore structure of the catalysts are believed to correlate with its high catalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Sediment Properties along Gradients of Siltation in South-East Asia
DEFF Research Database (Denmark)
Kamp-Nielsen, Lars; Vermaat, J.; Wesseling, I.
sediment properties, SE Asia, siltation, resuspension, iron, calcium, seagrass, corals, mangroves, mudflats......sediment properties, SE Asia, siltation, resuspension, iron, calcium, seagrass, corals, mangroves, mudflats...
Microbial Reduction of Fe(III) and SO42- and Associated Microbial Communities in the Alluvial Aquifer Groundwater and Sediments.
Lee, Ji-Hoon; Lee, Bong-Joo
Agricultural demands continuously increased use of groundwater, causing drawdown of water table and need of artificial recharge using adjacent stream waters. River water intrusion into groundwater can alter the geochemical and microbiological characteristics in the aquifer and subsurface. In an effort to investigate the subsurface biogeochemical activities before operation of artificial recharge at the test site, established at the bank of Nakdong River, Changwon, South Korea, organic carbon transported from river water to groundwater was mimicked and the effect on the indigenous microbial communities was investigated with the microcosm incubations of the groundwater and subsurface sediments. Laboratory incubations indicated microbial reduction of Fe(III) and sulfate. Next-generation Illumina MiSeq sequences of V4 region of 16S rRNA gene provided that the shifts of microbial taxa to Fe(III)-reducing and/or sulfate-reducing microorganisms such as Geobacter, Albidiferax, Desulfocapsa, Desulfuromonas, and Desulfovibrio were in good correlation with the sequential flourishment of microbial reduction of Fe(III) and sulfate as the incubations progressed. This suggests the potential role of dissolved organic carbons migrated with the river water into groundwater in the managed aquifer recharge system on the indigenous microbial community composition and following alterations of subsurface biogeochemistry and microbial metabolic activities.
Iron-coupled inactivation of phosphorus in sediments by macrozoobenthos (chironomid larvae) bioturbation: Evidences from high-resolution dynamic measurements
International Nuclear Information System (INIS)
Chen, Musong; Ding, Shiming; Liu, Ling; Xu, Di; Han, Chao; Zhang, Chaosheng
The effects of chironomid larvae bioturbation on the lability of phosphorus (P) in sediments were investigated through sediment incubation for 140 days. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were applied to obtain soluble and labile P/Fe profiles at a millimeter resolution, respectively. The larvae bioturbation decreased concentrations of soluble/labile P and Fe by up to over half of the control at the sediment depths of influence up to 70 and 90 mm respectively. These effects continued over 116 days and disappeared on the 140th days due to eclosion of chironomid larvae. Labile P was highly correlated with labile Fe, while a weak correlation was observed between soluble P and soluble Fe. It was concluded that Fe(II) oxidation and its enhanced adsorption were the major mechanisms responsible for the decreases of soluble and labile P. - Highlights: • High resolution techniques were employed to study bioturbation effects on P. • Larvae bioturbation decreased the concentrations of soluble/labile P and Fe. • Bioturbation effects continued over 116 days and disappeared on the 140th days. • Labile P was more sensitive than pore water SRP in response to bioturbation. • It proved the mechanism of Fe-coupled inactivation of P in bioturbation sediments. - Chironomid larvae bioturation decreased the lability of P in sediments from Fe(II) oxidation and enhanced adsorption of P
Role of sulfate reduction and methane production by organic carbon degradation ineutrophic fjord sediments (Limfjorden, Denmark)
DEFF Research Database (Denmark)
Jørgensen, Bo Barker; Parkes, R. John
, accompanied by peaks in sulfide (4-6 mmol L21) and high dissolved inorganic carbon (30-50 mmol L21). Pore-water acetate concentrations were 2-10 mmol L21. 14C-acetate was oxidized to 14CO2 in the sulfate zone and reduced to 14CH4 at and below the SMT. CO2 reduction was the predominant pathway....... A comparison of the burial flux of organic carbon below the sulfate zone and the returning flux of methane indicated that the diffusion modeling of pore-water sulfate strongly underestimated in situ SRRs, whereas the 35S data may have overestimated the rates at depth. Modeled and measured SRR could...
Greenhouse Gas Mitigation Options in ISEEM Global Energy Model: 2010-2050 Scenario Analysis for Least-Cost Carbon Reduction in Iron and Steel Sector
Energy Technology Data Exchange (ETDEWEB)
Karali, Nihan; Xu, Tengfang; Sathaye, Jayant
The goal of the modeling work carried out in this project was to quantify long-term scenarios for the future emission reduction potentials in the iron and steel sector. The main focus of the project is to examine the impacts of carbon reduction options in the U.S. iron and steel sector under a set of selected scenarios. In order to advance the understanding of carbon emission reduction potential on the national and global scales, and to evaluate the regional impacts of potential U.S. mitigation strategies (e.g., commodity and carbon trading), we also included and examined the carbon reduction scenarios in China's and India's iron and steel sectors in this project. For this purpose, a new bottom-up energy modeling framework, the Industrial Sector Energy Efficiency Modeling (ISEEM), (Karali et al. 2012) was used to provide detailed annual projections starting from 2010 through 2050. We used the ISEEM modeling framework to carry out detailed analysis, on a country-by-country basis, for the U.S., China's, and India's iron and steel sectors. The ISEEM model applicable to iron and steel section, called ISEEM-IS, is developed to estimate and evaluate carbon emissions scenarios under several alternative mitigation options - including policies (e.g., carbon caps), commodity trading, and carbon trading. The projections will help us to better understand emission reduction potentials with technological and economic implications. The database for input of ISEEM-IS model consists of data and information compiled from various resources such as World Steel Association (WSA), the U.S. Geological Survey (USGS), China Steel Year Books, India Bureau of Mines (IBM), Energy Information Administration (EIA), and recent LBNL studies on bottom-up techno-economic analysis of energy efficiency measures in the iron and steel sector of the U.S., China, and India, including long-term steel production in China. In the ISEEM-IS model, production technology and manufacturing details are
Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile
DEFF Research Database (Denmark)
Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker
suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....
Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems
Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia
We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.
Seasonal Arsenic Accumulation in Stream Sediments at a Groundwater Discharge Zone
DEFF Research Database (Denmark)
MacKay, Allison A.; Gan, Ping; Yu, Ran
Seasonal changes in arsenic and iron accumulation rates were examined in the sediments of a brook that receives groundwater discharges of arsenic and reduced iron. Clean glass bead columns were deployed in sediments for known periods over the annual hydrologic cycle to monitor changes in arsenic...... and iron concentrations in bead coatings. The highest accumulation rates occurred during the dry summer period (July-October) when groundwater discharges were likely greatest at the sample locations. The intermediate flow period (October-March), With higher surface water: levels, was associated with losses...... of arsenic and iron from bead column coatings at. depths below 2-6 cm. Batch incubations indicated iron releases from solids to be induced by biological reduction of iron (oxy)hydroxide solids. Congruent arsenic releases during incubation were limited by the high arsenic sorption capacity (0.536 mg...
A Mesoproterozoic iron formation
Canfield, Donald E.; Zhang, Shuichang; Wang, Huajian; Wang, Xiaomei; Zhao, Wenzhi; Su, Jin; Bjerrum, Christian J.; Haxen, Emma R.; Hammarlund, Emma U.
We describe a 1,400 million-year old (Ma) iron formation (IF) from the Xiamaling Formation of the North China Craton. We estimate this IF to have contained at least 520 gigatons of authigenic Fe, comparable in size to many IFs of the Paleoproterozoic Era (2,500–1,600 Ma). Therefore, substantial IFs formed in the time window between 1,800 and 800 Ma, where they are generally believed to have been absent. The Xiamaling IF is of exceptionally low thermal maturity, allowing the preservation of organic biomarkers and an unprecedented view of iron-cycle dynamics during IF emplacement. We identify tetramethyl aryl isoprenoid (TMAI) biomarkers linked to anoxygenic photosynthetic bacteria and thus phototrophic Fe oxidation. Although we cannot rule out other pathways of Fe oxidation, iron and organic matter likely deposited to the sediment in a ratio similar to that expected for anoxygenic photosynthesis. Fe reduction was likely a dominant and efficient pathway of organic matter mineralization, as indicated by organic matter maturation by Rock Eval pyrolysis combined with carbon isotope analyses: Indeed, Fe reduction was seemingly as efficient as oxic respiration. Overall, this Mesoproterozoic-aged IF shows many similarities to Archean-aged (>2,500 Ma) banded IFs (BIFs), but with an exceptional state of preservation, allowing an unprecedented exploration of Fe-cycle dynamics in IF deposition.
Thiosulfate and Sulfite Distributions in Porewater of Marine-Sediments Related to Manganese, Iron, and Sulfur Geochemistry
DEFF Research Database (Denmark)
Thamdrup, B; Finster, Kai; Fossing, Henrik
Depth distributions of thiosulfate (S2O32-) and sulfite (SO32-) were measured in the porewaters of a Danish salt marsh and subtidal marine sediments by HPLC analysis after derivatization with DTNP [2,2'-dithiobis(5-nitropyridine)]. The distributions were compared to the redox zonation as indicate...
Bioaccumulation of Iron and Lead in the soft tissue of some marine molluscs and associated sediment at labor Island,Aden,yemen
International Nuclear Information System (INIS)
Ali, Anis Ahmed; Baharoon Aqil Abdulrahman
The aim of this research work is to know the effect of the oil spill from the oil pipes that pass near the Labor Island, in addition the use of the Island as a station for gathering the old ships and boats that been prepared for re-exportation. For this purpose, a number of marine molluscs were used such as, A canthopleura haddoni (chitons), Ostrea cucullata (oysters), Turbo coronatus (sea snails). The were classified to their classes and sizes. Associated surfacial sediments were also used after sieving to <63 μm, in order to be analyzed by using the AAS. The results obtained showed high concentration in Fe and Pb in the soft tissue of the marine animals used and the associated sediment. These results indicate that these two heavy metals were bioaccumulated, and this accumulation may be returned to the oil spill from the oil pipes, or to the spill of drainage from the Iron mountain camp, or all the probabilities together. (author)
Selective recovery of nickel over iron from a nickel-iron solution using microbial sulfate reduction in a gas-lift bioreactor
Bijmans, M.F.M.; Helvoort, van P.J.; Dar, S.; Dopson, M.; Lens, P.N.L.; Buisman, C.J.N.
Process streams with high concentrations of metals and sulfate are characteristic for the mining and metallurgical industries. This study aims to selectively recover nickel from a nickel-iron-containing solution at pH 5.0 using a single stage bioreactor that simultaneously combines low pH sulfate
Inhibition of nitrate reduction by NaCl adsorption on a nano-zero-valent iron surface during a concentrate treatment for water reuse.
Hwang, Yuhoon; Kim, Dogun; Shin, Hang-Sik
Nanoscale zero-valent iron (NZVI) has been considered as a possible material to treat water and wastewater. However, it is necessary to verify the effect of the matrix components in different types of target water. In this study, different effects depending on the sodium chloride (NaCl) concentration on reductions of nitrates and on the characteristics of NZVI were investigated. Although NaCl is known as a promoter of iron corrosion, a high concentration of NaCl (>3 g/L) has a significant inhibition effect on the degree of NZVI reactivity towards nitrate. The experimental results were interpreted by a Langmuir-Hinshelwood-Hougen-Watson reaction in terms of inhibition, and the decreased NZVI reactivity could be explained by the increase in the inhibition constant. As a result of a chloride concentration analysis, it was verified that 7.7-26.5% of chloride was adsorbed onto the surface of NZVI. Moreover, the change of the iron corrosion product under different NaCl concentrations was investigated by a surface analysis of spent NZVI. Magnetite was the main product, with a low NaCl concentration (0.5 g/L), whereas amorphous iron hydroxide was observed at a high concentration (12 g/L). Though the surface was changed to permeable iron hydroxide, the Fe(0) in the core was not completely oxidized. Therefore, the inhibition effect of NaCl could be explained as the competitive adsorption of chloride and nitrate.
Improved thermooxidation and sedimentation stability of covalently-coated carbonyl iron particles with cholesteryl groups and their influence on magnetorheology
Czech Academy of Sciences Publication Activity Database
Mrlík, M.; Ilčíková, M.; Pavlínek, V.; Mosnáček, J.; Peer, Petra; Filip, Petr
Roč. 396, april (2013), s. 146-151 ISSN 0021-9797 R&D Projects: GA ČR GA202/09/1626 Grant - others:GA MŠk(CZ) ED2.1.00/03.0111 Institutional support: RVO:67985874 Keywords : covalent coating * carbonyl iron * cholesteryl chloroformate * thermooxidation * Magnetorheology Subject RIV: BK - Fluid Dynamics Impact factor: 3.552, year: 2013
Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media
Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian
Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.
Immobilization of Iron Nanoparticles on Multi Substrates and Its Reduction Removal of Chromium (VI) from Waste Streams
This article describes the in-situ synthesis and immobilization of iron nanoparticles on several substrates at room temperature using NaBH4 as a reducing agent and ascorbic acid as capping agent. The method is very effective in protecting iron nanoparticles from air oxidation for...
Impacts of crab bioturbation and local pollution on sulfate reduction, Hg distribution and methylation in mangrove sediments, Rio de Janeiro, Brazil.
Correia, Raquel Rose Silva; Guimarães, Jean Remy Davée
Mercury (Hg) and methylmercury (MeHg) are highly toxic and poorly studied in mangroves. Burrowing Uca crabs change sediment topography and biogeochemistry and thus may affect Hg distribution and MeHg formation. We studied added (203)Hg distribution, Me(203)Hg formation and sulfate reduction rates (SRR) in sediment aquariums containing Uca leptodactyla; and analyzed profiles of Me(203)Hg formation and SRR in sediment cores from two mangroves with distinct environmental impacts. MeHg formation and SRR were higher in the top (≤6cm) sediment and there was no significant difference in Hg methylation in more or less impacted mangroves. In aquariums, crab bioturbation favored Hg retention in the sediment. In the treatment without crabs, Hg volatilization and water Hg concentrations were higher. Hg methylation was higher in bioturbated aquariums but SRR were similar in both treatments. These findings suggest that bioturbating activity favors Hg retention in sediment but also promotes MeHg formation near the surface. Copyright © 2016 Elsevier Ltd. All rights reserved.
Reduction of metal exposure of Daubenton's bats (Myotis daubentonii) following remediation of pond sediment as evidenced by metal concentrations in hair.
Flache, Lucie; Ekschmitt, Klemens; Kierdorf, Uwe; Czarnecki, Sezin; Düring, Rolf-Alexander; Encarnação, Jorge A
Transfer of contaminants from freshwater sediments via aquatic insects to terrestrial predators is well documented in spiders and birds. Here, we analyzed the metal exposure of Myotis daubentonii using an urban pond as their preferred foraging area before and after a remediation measure (sediment dredging) at this pond. Six metal elements (Zn, Cu, Cr, Cd, Pb and Ni) were measured in the sediment of the pond, in EDTA extracts of the sediment and in hair samples of M. daubentonii foraging at the pond. Samples were taken before remediation in 2011 and after remediation in 2013. Metal concentrations were quantified by ICP-OES after miniaturized microwave assisted extraction. In 2011, the pond sediment exhibited a high contamination with nickel, a moderate contamination with copper and chromium and low contents of zinc, cadmium and lead. While sediment metal contents declined only weakly after remediation, a much more pronounced reduction in the concentrations of zinc, copper, chromium and lead concentrations was observed in bat hair. Our results suggest a marked decline in metal exposure of the bats foraging at the pond as a consequence of the remediation measure. It is concluded that Daubenton's bats are suitable bioindicators of metal contamination in aquatic environments, integrating metal exposure via prey insects over their entire foraging area. We further suggest that bat hair is a useful monitoring unit, allowing a non-destructive and non-invasive assessment of metal exposure in bats. Copyright © 2015 Elsevier B.V. All rights reserved.
Effect of dissimilatory iron and sulfate reduction on arsenic dynamics in the wetland rhizosphere and its bioaccumulation in plants
Jaffe, P. R.; Zhang, Z.; Moon, H. S.; Myneni, S.
The mobility of arsenic in soils is linked to biogeochemical redox processes. The presence of wetland plants in riparian wetlands has a significant impact on the biogeochemical dynamics of the soil/sediment-redoxcline due to the release of root exudates and root turnover and oxygen transfer from the roots into the surrounding sediment. Micro-environmental redox conditions in the rhizosphere affect As, Fe, and S speciation as well as Fe(III) plaque deposition, which affects arsenic transport and uptake by plants. To investigate the dynamics of As coupled to S and Fe cycling in wetlands, mesocosms were operated in a greenhouse under various conditions (high and low Fe, high and low sulfate, with plant and without plants) for four months. Results show that the presence of plants, high Fe, and high SO42- levels enhanced As sequestration in these soils. We hypothesize that this compounding effect is because plants release biodegradable organic carbon, which is used by microorganism to reduce ferrihydrite and SO42- to generate FeS, FeS2, and/or orpiment (As2S3). Over the concentration range studied, As immobilization in soil and uptake by Scirpus actus was mainly controlled by SO42- rather than Fe levels. Under high sulfate levels, As immobilization in soil increased by 50% and As concentrations in plant roots increased by 97%, whereas no significant changes in plant As levels were seen for varying Fe concentrations. More than 80% of As was sequestrated in soils rather than plant uptake. Pore water As speciation analyses indicate that 20% more As(V) was reduced to As(III) under high sulfate as than low sulfate levels and that low Fe was more favorable to the As dissimilatory reduction. More dissimilatory arsenate-respiring bacteria (DARB) under high sulfate were confirmed by quantitative PCR. Arsenic distribution in plant leafs and roots after 30 days of exposure to As was analyzed via Synchrotron X-ray fluorescence analyses. The uptake of As by plants was distributed
Sulphate reduction and vertical distribution of sulphate-reducing bacteria quantified by rRNA slot-blot hybridization in a coastal marine sediment
DEFF Research Database (Denmark)
Sahm, K.; MacGregor, BJ; Jørgensen, BB
In the past, enumeration of sulphate-reducing bacteria (SRB) by cultivation-based methods generally contradicted measurements of sulphate reduction, suggesting unrealistically high respiration rates per cell. Here, we report evidence that quantification of SRB rRNA by slot-blot hybridization......, directly above the sulphate reduction maximum. Cell numbers calculated by converting the relative contribution of SRB rRNA to the percentage of DAPI-stained cells indicated a population size for SRB of 2.4-6.1 x 10(8) cells cm(-3) wet sediment. Cellular sulphate reduction rates calculated on the basis...
When soils become sediments: Large-scale storage of soils in sandpits and lakes and the impact of reduction kinetics on heavy metals and arsenic release to groundwater.
Vink, Jos P M; van Zomeren, Andre; Dijkstra, Joris J; Comans, Rob N J
Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl 2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water. Copyright © 2017 Elsevier Ltd. All rights reserved.
Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method
International Nuclear Information System (INIS)
This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 2. of ISO 7097 describes procedures for determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with cerium(IV) and ISO 7097-1 uses a titration with potassium dichromate
Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids - Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method
International Nuclear Information System (INIS)
This first edition of ISO 7097-1 together with ISO 7097-2:2004 cancels and replaces ISO 7097:1983, which has been technically revised, and ISO 9989:1996. ISO 7097 consists of the following parts, under the general title Nuclear fuel technology - Determination of uranium in solutions, uranium hexafluoride and solids: Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method; Part 2: Iron(II) reduction/cerium(IV) oxidation titrimetric method. This part 1. of ISO 7097 describes procedures for the determination of uranium in solutions, uranium hexafluoride and solids. The procedures described in the two independent parts of this International Standard are similar: this part uses a titration with potassium dichromate and ISO 7097-2 uses a titration with cerium(IV)
Total Reducing Capacity in Aquifer Minerals and Sediments: Quantifying the Potential to Attenuate Cr(VI) in Groundwater
International Nuclear Information System (INIS)
Sisman, S. Lara
Hexavalent chromium, Cr(VI), is present in the environment as a byproduct of industrial processes. Due to its mobility and toxicity, it is crucial to attenuate or remove Cr(VI) from the environment. The objective of this investigation was to quantify potential natural attenuation, or reduction capacity, of reactive minerals and aquifer sediments. Samples of reduced-iron containing minerals such as ilmenite, as well as Puye Formation sediments representing a contaminated aquifer in New Mexico, were reacted with chromate. The change in Cr(VI) during the reaction was used to calculate reduction capacity. This study found that minerals that contain reduced iron, such as ilmenite, have high reducing capacities. The data indicated that sample history may impact reduction capacity tests due to surface passivation. Further, this investigation identified areas for future research including: a) refining the relationships between iron content, magnetic susceptibility and reduction capacity, and b) long term kinetic testing using fresh aquifer sediments.
Total Reducing Capacity in Aquifer Minerals and Sediments: Quantifying the Potential to Attenuate Cr(VI) in Groundwater
Energy Technology Data Exchange (ETDEWEB)
Sisman, S. Lara [Univ. of Virginia, Charlottesville, VA (United States); Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)
Hexavalent chromium, Cr(VI), is present in the environment as a byproduct of industrial processes. Due to its mobility and toxicity, it is crucial to attenuate or remove Cr(VI) from the environment. The objective of this investigation was to quantify potential natural attenuation, or reduction capacity, of reactive minerals and aquifer sediments. Samples of reduced-iron containing minerals such as ilmenite, as well as Puye Formation sediments representing a contaminated aquifer in New Mexico, were reacted with chromate. The change in Cr(VI) during the reaction was used to calculate reduction capacity. This study found that minerals that contain reduced iron, such as ilmenite, have high reducing capacities. The data indicated that sample history may impact reduction capacity tests due to surface passivation. Further, this investigation identified areas for future research including: a) refining the relationships between iron content, magnetic susceptibility and reduction capacity, and b) long term kinetic testing using fresh aquifer sediments.
Archaeal diversity and the extent of iron and manganese pyritization in sediments from a tropical mangrove creek (Cardoso Island, Brazil)
Otero, X. L.; Lucheta, A. R.; Ferreira, T. O.; Huerta-Díaz, M. A.; Lambais, M. R.
Even though several studies on the geochemical processes occurring in mangrove soils and sediments have been performed, information on the diversity of Archaea and their functional roles in these ecosystems, especially in subsurface environments, is scarce. In this study, we have analyzed the depth distribution of Archaea and their possible relationships with the geochemical transformations of Fe and Mn in a sediment core from a tropical mangrove creek, using 16S rRNA gene profiling and sequential extraction of different forms of Fe and Mn. A significant shift in the archaeal community structure was observed in the lower layers (90-100 cm), coinciding with a clear decrease in total organic carbon (TOC) content and an increase in the percentage of sand. The comparison of the archaeal communities showed a dominance of methanogenic Euryarchaeota in the upper layers (0-20 cm), whereas Crenarchaeota was the most abundant taxon in the lower layers. The dominance of methanogenic Euryarchaeota in the upper layer of the sediment suggests the occurrence of methanogenesis in anoxic microenvironments. The concentrations of Fe-oxyhydroxides in the profile were very low, and showed positive correlation with the concentrations of pyrite and degrees of Fe and Mn pyritization. Additionally, a partial decoupling of pyrite formation from organic matter concentration was observed, suggesting excessive Fe pyritization. This overpyritization of Fe can be explained either by the anoxic oxidation of methane by sulfate and/or by detrital pyrite tidal transportation from the surrounding mangrove soils. The higher pyritization levels observed in deeper layers of the creek sediment were also in agreement with its Pleistocenic origin.
Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model
International Nuclear Information System (INIS)
Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Rod, Kenton A.
Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent-sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO U O 2 HCO 3 and SO U O 2 OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions
Viable cold-tolerant iron-reducing microorganisms in geographically diverse subglacial environments
Nixon, Sophie L.; Telling, Jon P.; Wadham, Jemma L.; Cockell, Charles S.
Subglacial environments are known to harbour metabolically diverse microbial communities. These microbial communities drive chemical weathering of underlying bedrock and influence the geochemistry of glacial meltwater. Despite its importance in weathering reactions, the microbial cycling of iron in subglacial environments, in particular the role of microbial iron reduction, is poorly understood. In this study we address the prevalence of viable iron-reducing microorganisms in subglacial sediments from five geographically isolated glaciers. Iron-reducing enrichment cultures were established with sediment from beneath Engabreen (Norway), Finsterwalderbreen (Svalbard), Leverett and Russell glaciers (Greenland), and Lower Wright Glacier (Antarctica). Rates of iron reduction were higher at 4 °C compared with 15 °C in all but one duplicated second-generation enrichment culture, indicative of cold-tolerant and perhaps cold-adapted iron reducers. Analysis of bacterial 16S rRNA genes indicates Desulfosporosinus were the dominant iron-reducing microorganisms in low-temperature Engabreen, Finsterwalderbreen and Lower Wright Glacier enrichments, and Geobacter dominated in Russell and Leverett enrichments. Results from this study suggest microbial iron reduction is widespread in subglacial environments and may have important implications for global biogeochemical iron cycling and export to marine ecosystems.
Fabrication of iron-doped cobalt oxide nanocomposite films by electrodeposition and application as electrocatalyst for oxygen reduction reaction
Energy Technology Data Exchange (ETDEWEB)
Zhang, Jingxuan; Wang, Xuemei; Qin, Dongdong; Xue, Zhonghua; Lu, Xiaoquan, E-mail: firstname.lastname@example.com
Highlights: • We fabricated the Fe-doped Co{sub 3}O{sub 4} nanofilms for the first time by potentiostatic electrodeposition method. • The Fe was doped homogeneously in the nanofilms by this method. • Among the different concentration ratios of Co{sup 2+}/Fe{sup 2+}, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. • The Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit good electrocatalytic activity toward oxygen reduction and appear to be promising cathodic electrocatalyst in alkaline fuel cells. - Abstract: In this work, Fe-doped Co{sub 3}O{sub 4} nanofilms were fabricated by electrodeposition on FTO glass substrates for the first time. The structures of the as-prepared nanofilms were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Characterization results demonstrate that Fe was doped homogeneously in the nanofilms. As the different concentration ratios of Fe{sup 2+}/Co{sup 2+} were explored, nanofilm with the ratio of 1:5 exhibits the optimal performance in electrochemical properties assessments. It is considered that the difference in the catalytic activities for the ORR of the samples may be due to the fact that the joining of iron changed the catalyst surface's electric state and enhanced the acidity of cobalt centers, on the other hand, the doping process probably modified the absorption property of the nanofilms. The experimental results suggest that the Fe-doped Co{sub 3}O{sub 4} nanofilms in this work exhibit favorable electrocatalytic activity toward ORR and appear to be promising cathodic electrocatalyst in alkaline fuel cells.
Fluvial geomorphology and suspended-sediment transport during construction of the Roanoke River Flood Reduction Project in Roanoke, Virginia, 2005–2012
Jastram, John D.; Krstolic, Jennifer L.; Moyer, Douglas; Hyer, Kenneth
Beginning in 2005, after decades of planning, the U.S. Army Corps of Engineers (USACE) undertook a major construction effort to reduce the effects of flooding on the city of Roanoke, Virginia—the Roanoke River Flood Reduction Project (RRFRP). Prompted by concerns about the potential for RRFRP construction-induced geomorphological instability and sediment liberation and the detrimental effects these responses could have on the endangered Roanoke logperch (Percina rex), the U.S. Geological Survey (USGS) partnered with the USACE to provide a real-time warning network and a long-term monitoring program to evaluate geomorphological change and sediment transport in the affected river reach. Geomorphological change and suspended-sediment transport are highly interdependent and cumulatively provide a detailed understanding of the sedimentary response, or lack thereof, of the Roanoke River to construction of the RRFRP.
Electron-beam-induced reduction of Fe3+ in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy
International Nuclear Information System (INIS)
Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik; Bleloch, Andrew; Gass, Mhairi; Sader, Kasim; Brown, Andy
The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L 2,3 -ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H 2 O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.
Electron-beam-induced reduction of Fe{sup 3+} in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy
Energy Technology Data Exchange (ETDEWEB)
Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); Bleloch, Andrew; Gass, Mhairi [SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Sader, Kasim [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Brown, Andy, E-mail: firstname.lastname@example.com [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom)
The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L{sub 2,3}-ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H{sub 2}O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.
Reduction kinetics of Wüstite scale on pure iron and steel sheets in Ar and H
Mao, W.; Sloof, W.G.
A dense and closed Wüstite scale is formed on pure iron and Mn alloyed steel after oxidation in Ar + 33 vol pct CO2 + 17 vol pct CO gas mixture. Reducing the Wüstite scale in Ar + H2 gas mixture forms a dense and uniform iron layer on top of the remaining Wüstite scale,
Microbial reduction of ferric iron oxyhydroxides as a way for remediation of grey forest soils heavily polluted with toxic metals by infiltration of acid mine drainage
Georgiev, Plamen; Groudev, Stoyan; Spasova, Irena; Nicolova, Marina
The abandoned uranium mine Curilo is a permanent source of acid mine drainage (AMD) which steadily contaminated grey forest soils in the area. As a result, the soil pH was highly acidic and the concentration of copper, lead, arsenic, and uranium in the topsoil was higher than the relevant Maximum Admissible Concentration (MAC) for soils. The leaching test revealed that approximately half of each pollutant was presented as a reducible fraction as well as the ferric iron in horizon A was presented mainly as minerals with amorphous structure. So, the approach for remediation of the AMD-affected soils was based on the process of redoxolysis carried out by iron-reducing bacteria. Ferric iron hydroxides reduction and the heavy metals released into soil solutions was studied in the dependence on the source of organic (fresh or silage hay) which was used for growth and activity of soil microflora, initial soil pH (3.65; 4.2; and 5.1), and the ion content of irrigation solutions. The combination of limestone (2.0 g/ kg soil), silage addition (at rate of 45 g dry weight/ kg soil) in the beginning and reiterated at 6 month since the start of soil remediation, and periodical soil irrigation with slightly acidic solutions containing CaCl2 was sufficient the content of lead and arsenic in horizon A to be decreased to concentrations similar to the relevant MAC. The reducible, exchangeable, and carbonate mobile fractions were phases from which the pollutants was leached during the applied soil remediation. It determined the higher reduction of the pollutants bioavailability also as well as the process of ferric iron reduction was combined with neutralization of the soil acidity to pH (H2O) 6.2.
Microcosm studies on iron and arsenic mobilization from aquifer sediments under different conditions of microbial activity and carbon source
Duan, Mengyu; Xie, Zuoming; Wang, Yanxin; Xie, Xianjun
Microcosm experiments were conducted to understand the mechanism of microbially mediated mobilization of Fe and As from high arsenic aquifer sediments. Arsenic-resistant strains isolated from aquifer sediments of a borehole specifically drilled for this study at Datong basin were used as inoculated strains, and glucose and sodium acetate as carbon sources for the experiments. In abiotic control experiments, the maximum concentrations of Fe and As were only 0.47 mg/L and 0.9 μg/L, respectively. By contrast, the maximum contents of Fe and As in anaerobic microcosm experiments were much higher (up to 1.82 mg/L and 12.91 μg/L, respectively), indicating the crucial roles of microbial activities in Fe and As mobilization. The observed difference in Fe and As release with different carbon sources may be related to the difference in growth pattern and composition of microbial communities that develop in response to the type of carbon sources.
The pH and pCO2 dependence of sulfate reduction in shallow-sea hydrothermal CO2 – venting sediments (Milos Island, Greece)
Bayraktarov, Elisa; Price, Roy E.; Ferdelman, Timothy G.; Finster, Kai
Microbial sulfate reduction (SR) is a dominant process of organic matter mineralization in sulfate-rich anoxic environments at neutral pH. Recent studies have demonstrated SR in low pH environments, but investigations on the microbial activity at variable pH and CO2 partial pressure are still lacking. In this study, the effect of pH and pCO2 on microbial activity was investigated by incubation experiments with radioactive 35S targeting SR in sediments from the shallow-sea hydrothermal vent system of Milos, Greece, where pH is naturally decreased by CO2 release. Sediments differed in their physicochemical characteristics with distance from the main site of fluid discharge. Adjacent to the vent site (T ~40–75°C, pH ~5), maximal sulfate reduction rates (SRR) were observed between pH 5 and 6. SR in hydrothermally influenced sediments decreased at neutral pH. Sediments unaffected by hydrothermal venting (T ~26°C, pH ~8) expressed the highest SRR between pH 6 and 7. Further experiments investigating the effect of pCO2 on SR revealed a steep decrease in activity when the partial pressure increased from 2 to 3 bar. Findings suggest that sulfate reducing microbial communities associated with hydrothermal vent system are adapted to low pH and high CO2, while communities at control sites required a higher pH for optimal activity. PMID:23658555
The pH and pCO2 dependence of sulfate reduction in shallow-sea hydrothermal CO2 - venting sediments (Milos Island, Greece).
Bayraktarov, Elisa; Price, Roy E; Ferdelman, Timothy G; Finster, Kai
Microbial sulfate reduction (SR) is a dominant process of organic matter mineralization in sulfate-rich anoxic environments at neutral pH. Recent studies have demonstrated SR in low pH environments, but investigations on the microbial activity at variable pH and CO2 partial pressure are still lacking. In this study, the effect of pH and pCO2 on microbial activity was investigated by incubation experiments with radioactive (35)S targeting SR in sediments from the shallow-sea hydrothermal vent system of Milos, Greece, where pH is naturally decreased by CO2 release. Sediments differed in their physicochemical characteristics with distance from the main site of fluid discharge. Adjacent to the vent site (T ~40-75°C, pH ~5), maximal sulfate reduction rates (SRR) were observed between pH 5 and 6. SR in hydrothermally influenced sediments decreased at neutral pH. Sediments unaffected by hydrothermal venting (T ~26°C, pH ~8) expressed the highest SRR between pH 6 and 7. Further experiments investigating the effect of pCO2 on SR revealed a steep decrease in activity when the partial pressure increased from 2 to 3 bar. Findings suggest that sulfate reducing microbial communities associated with hydrothermal vent system are adapted to low pH and high CO2, while communities at control sites required a higher pH for optimal activity.
Heterojunction nanowires having high activity and stability for the reduction of oxygen: Formation by self-assembly of iron phthalocyanine with single walled carbon nanotubes (FePc/SWNTs)
Zhu, Jia; Jia, Nana; Yang, Lijun; Su, Dong; Park, Jinseong; Choi, YongMan; Gong, Kuanping
A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1
Possible Links Among Iron Reduction, Silicate Weathering, and Arsenic Mobility in the Mississippi River Alluvial Aquifer in Louisiana
Borrok, D. M.; Lenz, R. M.; Jennings, J. E.; Gentry, M. L.; Vinson, D. S.
The Lower Mississippi River Alluvial Aquifer (LMRAA) is a critical groundwater resource for Arkansas, Mississippi, and Louisiana. Part of the aquifer in Louisiana contains waters rich in Na, HCO3, Fe, and As. We hypothesize that CO2 generated from dissimilatory iron reduction (DIR) within the aquifer acts to weather Na-bearing silicates, contributing Na and HCO3, which may influence the mobility of As. We examined the geochemistry of the aquifer using historical and new data collected from the Louisiana Department of Environmental Quality (LDEQ). Major and trace element data were collected from about 25 wells in the LMRAA in Louisiana every three years from 2001-2016. Samples collected in 2016 were additionally analyzed for water isotopes and the δ13C of dissolved inorganic carbon (DIC). Results suggest that groundwater in the LMRAA can be broken into two broad categories, (1) water with a molar Na/Cl ratio near 1 and/or high salinity, and (2) water with excess Na (i.e., the molar concentration of Na is greater than that of Cl) that is often higher in alkalinity (up to 616 mg/L as CaCO3), Fe (up to 21 mg/L), and sometimes As (up to 67 µg/L). Concentrations of dissolved Fe were found to correlate, at least weakly, with alkalinity and Na excess. Six of the approximately 25 wells historically sampled consistently had concentrations of As >10 µg/L. These locations generally correspond with groundwater characterized by higher Fe, alkalinity, and Na-excess. Initial results for δD and δ18O suggest that more isotopically depleted waters are sourced from the Mississippi River, whereas local precipitation recharges the aquifer farther from the river (δ18O ranged from -7.5‰ to -3.5‰). Part of the δ13C-DIC variation (-17.4‰ to -10.6‰) is consistent with pH modification (6.5-7.7) along differing horizontal and vertical flow paths in the aquifer. This geochemistry appears to be controlled in part by geology. Areas nearer to the current Mississippi River where
Performance of nanoscale zero-valent iron in nitrate reduction from water using a laboratory-scale continuous-flow system.
Khalil, Ahmed M E; Eljamal, Osama; Saha, Bidyut Baran; Matsunaga, Nobuhiro
Nanoscale zero-valent iron (nZVI) is a versatile treatment reagent that should be utilized in an effective application for nitrate remediation in water. For this purpose, a laboratory-scale continuous-flow system (LSCFS) was developed to evaluate nZVI performance in removal of nitrate in different contaminated-water bodies. The equipment design (reactor, settler, and polisher) and operational parameters of the LSCFS were determined based on nZVI characterization and nitrate reduction kinetics. Ten experimental runs were conducted at different dosages (6, 10 and 20 g) of nZVI-based reagents (nZVI, bimetallic nZVI-Cu, CuCl 2 -added nZVI). Effluent concentrations of nitrogen and iron compounds were measured, and pH and ORP values were monitored. The major role exhibited by the recirculation process of unreacted nZVI from the settler to the reactor succeeded in achieving overall nitrate removal efficiency (RE) of >90%. The similar performance of both nZVI and copper-ions-modified nZVI in contaminated distilled water was an indication of LSCFS reliability in completely utilizing iron nanoparticles. In case of treating contaminated river water and simulated groundwater, the nitrate reduction process was sensitive towards the presence of interfering substances that dropped the overall RE drastically. However, the addition of copper ions during the treatment counteracted the retardation effect and greatly enhanced the nitrate RE. Copyright © 2018 Elsevier Ltd. All rights reserved.
Long term energy and materials strategies for reduction of industrial CO2 emissions. A case study for the iron and steel industry
International Nuclear Information System (INIS)
Gielen, D.J.
Greenhouse gas emissions emerged in the last decade as a key environmental problem on the political agenda. The most important greenhouse gas is carbon dioxide (CO 2 ). This gas results from the combustion of fossil fuels (natural gas, oil and coal). As a consequence, greenhouse gas emission reduction is closely related to energy policies. Even a stabilization of the atmospheric CO 2 concentrations at a level of 750 ppm (parts per million), more than twice the current level, implies a reduction of global emissions by 50% in the next century. The world population will simultaneously double and the capita energy consumption will increase. As a consequence, the Western industrialized countries will have to reduce their per capita emissions by more than a factor four. Such a policy goal will significantly affect the future industrial production structure. Approximately 4% of the global CO 2 emissions can be attributed to the production of iron and steel. This sector is the most important industrial source of CO 2 . The case study for the iron and steel industry will be discussed in this paper in order to illustrate the impact of significant CO 2 emission mitigation on the industry. The goal is to show the consequences of CO 2 policies for R and D planning and investment decisions. The notion that the iron and steel industry will be affected by CO 2 policies is not new; a number of studies have addressed this issue before. These studies have compared steel production technologies and emission reduction options within the iron and steel production sector. In this paper, the emission reduction in the iron and steel industry is analyzed within the framework of the changing (inter-)national energy and materials system configuration. This includes all production, conversion and consumption processes. The impact of CO 2 policies on the optimal choice of steel production technologies and on the competitiveness of steel compared to other materials will be discussed. This paper
Effect of organic enrichment and thermal regime on denitrification and dissimilatory nitrate reduction to ammonium (DNRA) in hypolimnetic sediments of two lowland lakes.
Nizzoli, Daniele; Carraro, Elisa; Nigro, Valentina; Viaroli, Pierluigi
We analyzed benthic fluxes of inorganic nitrogen, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) rates in hypolimnetic sediments of lowland lakes. Two neighbouring mesotrophic (Ca' Stanga; CS) and hypertrophic (Lago Verde; LV) lakes, which originated from sand and gravel mining, were considered. Lakes are affected by high nitrate loads (0.2-0.7 mM) and different organic loads. Oxygen consumption, dissolved inorganic carbon, methane and nitrogen fluxes, denitrification and DNRA were measured under summer thermal stratification and late winter overturn. Hypolimnetic sediments of CS were a net sink of dissolved inorganic nitrogen (-3.5 to -4.7 mmol m(-2)d(-1)) in both seasons due to high nitrate consumption. On the contrary, LV sediments turned from being a net sink during winter overturn (-3.5 mmol m(-2)d(-1)) to a net source of dissolved inorganic nitrogen under summer conditions (8.1 mmol m(-2)d(-1)), when significant ammonium regeneration was measured at the water-sediment interface. Benthic denitrification (0.7-4.1 mmol m(-2)d(-1)) accounted for up to 84-97% of total NO(3)(-) reduction and from 2 to 30% of carbon mineralization. It was mainly fuelled by water column nitrate. In CS, denitrification rates were similar in winter and in summer, while in LV summer rates were 4 times lower. DNRA rates were generally low in both lakes (0.07-0.12 mmol m(-2)d(-1)). An appreciable contribution of DNRA was only detected in the more reducing sediments of LV in summer (15% of total NO(3)(-) reduction), while during the same period only 3% of reduced NO(3)(-) was recycled into ammonium in CS. Under summer stratification benthic denitrification was mainly nitrate-limited due to nitrate depletion in hypolimnetic waters and parallel oxygen depletion, hampering nitrification. Organic enrichment and reducing conditions in the hypolimnetic sediment shifted nitrate reduction towards more pronounced DNRA, which resulted in the inorganic nitrogen recycling and
Sulphate reduction and vertical distribution of sulphate-reducing bacteria quantified by rRNA slot-blot hybridization in a coastal marine sediment
DEFF Research Database (Denmark)
Sahm, K.; MacGregor, BJ; Jørgensen, BB
In the past, enumeration of sulphate-reducing bacteria (SRB) by cultivation-based methods generally contradicted measurements of sulphate reduction, suggesting unrealistically high respiration rates per cell. Here, we report evidence that quantification of SRB rRNA by slot-blot hybridization...... between 18% and 25% to the prokaryotic rRNA pool. The dominant SRB were related to complete oxidizing genera (Desulphococcus, Desulphosarcina and Desulphobacterium), while Desulpho-bacter could not be detected. The vertical profile and quantity of rRNA from SRB was compared with sulphate reduction rates......, directly above the sulphate reduction maximum. Cell numbers calculated by converting the relative contribution of SRB rRNA to the percentage of DAPI-stained cells indicated a population size for SRB of 2.4-6.1 x 10(8) cells cm(-3) wet sediment. Cellular sulphate reduction rates calculated on the basis...
Stabilization of aqueous nanoscale zerovalent iron dispersions by anionic polyelectrolytes: adsorbed anionic polyelectrolyte layer properties and their effect on aggregation and sedimentation
International Nuclear Information System (INIS)
Phenrat, Tanapon; Saleh, Navid; Sirk, Kevin; Kim, Hye-Jin; Tilton, Robert D.; Lowry, Gregory V.
Nanoscale zerovalent iron (NZVI) particles are 5-40 nm sized Fe 0 /Fe-oxide particles that rapidly transform many environmental contaminants to benign products and are a promising in situ remediation agent. Rapid aggregation and limited mobility in water-saturated porous media limits the ability to deliver NZVI dispersions in the subsurface. This study prepares stable NZVI dispersions through physisorption of commercially available anionic polyelectrolytes, characterizes the adsorbed polymer layer, and correlates the polymer coating properties with the ability to prevent rapid aggregation and sedimentation of NZVI dispersions. Poly(styrene sulfonate) with molecular weights of 70 k and 1,000 k g/mol (PSS70K and PSS1M), carboxymethyl cellulose with molecular weights of 90 k and 700 k g/mol (CMC90K and CMC700K), and polyaspartate with molecular weights of 2.5 k and 10 k g/mol (PAP2.5K and 10K) were compared. Particle size distributions were determined by dynamic light scattering during aggregation. The order of effectiveness to prevent rapid aggregation and stabilize the dispersions was PSS70K(83%) > ∼PAP10K(82%) > PAP2.5K(72%) > CMC700K(52%), where stability is defined operationally as the volume percent of particles that do not aggregate after 1 h. CMC90K and PSS1M could not stabilize RNIP relative to bare RNIP. A similar trend was observed for their ability to prevent sedimentation, with 40, 34, 32, 20, and 5 wt%, of the PSS70K, PAP10K, PAP2.5K, CMC700K, and CMC90K modified NZVI remaining suspended after 7 h of quiescent settling, respectively. The stable fractions with respect to both aggregation and sedimentation correlate well with the adsorbed polyelectrolyte mass and thickness of the adsorbed polyelectrolyte layers as determined by Oshima's soft particle theory. A fraction of the particles cannot be stabilized by any modifier and rapidly agglomerates to micron sized aggregates, as is also observed for unmodified NZVI. This non-dispersible fraction is
Reduction and Immobilization of Radionuclides and Toxic Metal Ions Using Combined Zero Valent Iron and Anaerobic Bacteria
International Nuclear Information System (INIS)
Weathers, Lenly J.; Katz, Lynn E.
The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. AN exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes are functional. This work evaluated the hypothesis that a system combining a mixed culture of sulfate reducing bacteria (SRB) with zero valent iron would have a greater cr(VI) removal efficiency and a greater total Cr(VI) removal capacity than a zero valent iron system without the microorganisms. Hence, the overall goal of this research was to compare the performance of these types of systems with regard to their Cr(VI) removal efficiency and total Cr(VI) removal capacity. Both batch and continuous flow reactor systems were evaluated
Reduction and Immobilization of Radionuclides and Toxic Metal Ions Using Combined Zero Valent Iron and Anaerobic Bacteria; FINAL
International Nuclear Information System (INIS)
Lenly J. Weathers; Lynn E. Katz
The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. AN exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes are functional. This work evaluated the hypothesis that a system combining a mixed culture of sulfate reducing bacteria (SRB) with zero valent iron would have a greater cr(VI) removal efficiency and a greater total Cr(VI) removal capacity than a zero valent iron system without the microorganisms. Hence, the overall goal of this research was to compare the performance of these types of systems with regard to their Cr(VI) removal efficiency and total Cr(VI) removal capacity. Both batch and continuous flow reactor systems were evaluated
Reduction and Immobilization of Radionuclides and Toxic Metal Ions Using Combined Zero Valent Iron and Anaerobic Bacteria
Energy Technology Data Exchange (ETDEWEB)
Lenly J. Weathers; Lynn E. Katz
The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. AN exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes are functional. This work evaluated the hypothesis that a system combining a mixed culture of sulfate reducing bacteria (SRB) with zero valent iron would have a greater cr(VI) removal efficiency and a greater total Cr(VI) removal capacity than a zero valent iron system without the microorganisms. Hence, the overall goal of this research was to compare the performance of these types of systems with regard to their Cr(VI) removal efficiency and total Cr(VI) removal capacity. Both batch and continuous flow reactor systems were evaluated.
Empirical evidence reveals seasonally dependent reduction in nitrification in coastal sediments subjected to near future ocean acidification
Braeckman, U.; Van Colen, C.; Guilini, K.; Van Gansbeke, D.; Soetaert, K.; Vincx, M.; Vanaverbeke, J.
Research so far has provided little evidence that benthic biogeochemical cycling is affected by ocean acidification under realistic climate change scenarios. We measured nutrient exchange and sediment community oxygen consumption (SCOC) rates to estimate nitrification in natural coastal permeable
The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron.
Lewis, James M T; Najorka, Jens; Watson, Jonathan S; Sephton, Mark A
Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as "Hematite Ridge"), which may have formed from goethite precursors. Key Words: Mars-Pyrolysis-Jarosite-Goethite-Hematite-Biosignatures. Astrobiology 18, 454-464.
Reduction of metal exposure of Daubenton's bats (Myotis daubentonii) following remediation of pond sediment as evidenced by metal concentrations in hair
Energy Technology Data Exchange (ETDEWEB)
Flache, Lucie, E-mail: firstname.lastname@example.com [Mammalian Ecology Group, Department of Animal Ecology and Systematics, Justus Liebig University of Giessen, Heinrich-Buff-Ring 26, D-35392 Giessen (Germany); Ekschmitt, Klemens [Animal Ecology, Department of Animal Ecology and Systematics, Justus Liebig University of Giessen, Heinrich-Buff-Ring 26, D-35392 Giessen (Germany); Kierdorf, Uwe [Department of Biology, University of Hildesheim, Universitätsplatz 1, D-31141 Hildesheim (Germany); Czarnecki, Sezin; Düring, Rolf-Alexander [Institute of Soil Science and Soil Conservation, Justus Liebig University of Giessen, Heinrich-Buff-Ring 26, D-35392 Giessen (Germany); Encarnação, Jorge A. [Mammalian Ecology Group, Department of Animal Ecology and Systematics, Justus Liebig University of Giessen, Heinrich-Buff-Ring 26, D-35392 Giessen (Germany)
Transfer of contaminants from freshwater sediments via aquatic insects to terrestrial predators is well documented in spiders and birds. Here, we analyzed the metal exposure of Myotis daubentonii using an urban pond as their preferred foraging area before and after a remediation measure (sediment dredging) at this pond. Six metal elements (Zn, Cu, Cr, Cd, Pb and Ni) were measured in the sediment of the pond, in EDTA extracts of the sediment and in hair samples of M. daubentonii foraging at the pond. Samples were taken before remediation in 2011 and after remediation in 2013. Metal concentrations were quantified by ICP-OES after miniaturized microwave assisted extraction. In 2011, the pond sediment exhibited a high contamination with nickel, a moderate contamination with copper and chromium and low contents of zinc, cadmium and lead. While sediment metal contents declined only weakly after remediation, a much more pronounced reduction in the concentrations of zinc, copper, chromium and lead concentrations was observed in bat hair. Our results suggest a marked decline in metal exposure of the bats foraging at the pond as a consequence of the remediation measure. It is concluded that Daubenton's bats are suitable bioindicators of metal contamination in aquatic environments, integrating metal exposure via prey insects over their entire foraging area. We further suggest that bat hair is a useful monitoring unit, allowing a non-destructive and non-invasive assessment of metal exposure in bats. - Highlights: • Changes in metal exposure of bats due to remediation measure are documented. • Bats are suitable bioindicators of metal pollution. • Bat hair is a useful monitoring unit in such studies.
Reduction of metal exposure of Daubenton's bats (Myotis daubentonii) following remediation of pond sediment as evidenced by metal concentrations in hair
International Nuclear Information System (INIS)
Flache, Lucie; Ekschmitt, Klemens; Kierdorf, Uwe; Czarnecki, Sezin; Düring, Rolf-Alexander; Encarnação, Jorge A.
Transfer of contaminants from freshwater sediments via aquatic insects to terrestrial predators is well documented in spiders and birds. Here, we analyzed the metal exposure of Myotis daubentonii using an urban pond as their preferred foraging area before and after a remediation measure (sediment dredging) at this pond. Six metal elements (Zn, Cu, Cr, Cd, Pb and Ni) were measured in the sediment of the pond, in EDTA extracts of the sediment and in hair samples of M. daubentonii foraging at the pond. Samples were taken before remediation in 2011 and after remediation in 2013. Metal concentrations were quantified by ICP-OES after miniaturized microwave assisted extraction. In 2011, the pond sediment exhibited a high contamination with nickel, a moderate contamination with copper and chromium and low contents of zinc, cadmium and lead. While sediment metal contents declined only weakly after remediation, a much more pronounced reduction in the concentrations of zinc, copper, chromium and lead concentrations was observed in bat hair. Our results suggest a marked decline in metal exposure of the bats foraging at the pond as a consequence of the remediation measure. It is concluded that Daubenton's bats are suitable bioindicators of metal contamination in aquatic environments, integrating metal exposure via prey insects over their entire foraging area. We further suggest that bat hair is a useful monitoring unit, allowing a non-destructive and non-invasive assessment of metal exposure in bats. - Highlights: • Changes in metal exposure of bats due to remediation measure are documented. • Bats are suitable bioindicators of metal pollution. • Bat hair is a useful monitoring unit in such studies.
2-Nitrophenol reduction promoted by S. putrefaciens 200 and biogenic ferrous iron: The role of different size-fractions of dissolved organic matter
Energy Technology Data Exchange (ETDEWEB)
Zhu, Zhenke [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Tao, Liang, E-mail: email@example.com [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Li, Fangbai, E-mail: firstname.lastname@example.com [Guangdong Key Laboratory of Agricultural Environment Pollution Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China)
Graphical abstract: - Highlights: • Dissolved organic matter (DOM) act as electron shuttle in redox reactions. • Different molecular weight DOM fractions have different electron transfer capacity. • A higher electron transfer capacities value indicates a higher reduction rate. • DOM transfer electron from S. putrefaciens 200 to 2-nitrophenol (2-NP) and Fe(III). • DOM and biogenic Fe(II) synergistically enhanced the 2-NP reductive transformation. - Abstract: The reduction of nitroaromatic compounds (listed as a priority pollutant) in natural subsurface environments typically coexists with dissimilatory reduction of iron oxides effected by dissolved organic matter (DOM). Investigating the impact of the DOM that influences those reduction processes is crucial for understanding and predicting the geochemical fate of these environmental species. This study investigated the impact of different molecular weight DOM fractions (DMWDs) on the 2-nitrophenol (2-NP) reduction by S. putrefaciens 200 (SP200) and α-Fe{sub 2}O{sub 3} with lactate (excluding electron donor interference). Kinetic measurements demonstrated that 2-NP reduction rates were affected by the redox reactivity of active species under DMWDs (denoted as L-DOM, M-DOM, and H-DOM). The enhanced reduction rates are consistent with the negative shifts in peak oxidation potential values, the increases in HA-like/FA-like values, aromaticity index values and electron transfer capacity values. L-DOM acted mainly as ligands to complex Fe(II), whereas the significant role of H-DOM in reductive reactions should be acting as an electron shuttle, transferring electrons from SP200 to Fe(III) and 2-NP and from biogenic Fe(II) to 2-NP, further accelerating the 2-NP reductions. Those observations provide valuable insights into the role of DOM in the biogeochemical redox processes and the remediation of contaminated soil in a natural environment.
Reductive immobilization of U(VI) in Fe(III) oxide-reducing subsurface sediments: Analysis of coupled microbial-geochemical processes in experimental reactive transport systems. Final Scientific/Technical Report-EMSP 73914
International Nuclear Information System (INIS)
Eric E. Roden Matilde M. Urrutia Mark O. Barnett Clifford R. Lange
The purpose of this research was to provide information to DOE on microbiological and geochemical processes underlying the potential use of dissimilatory metal-reducing bacteria (DMRB) to create subsurface redox barriers for immobilization of uranium and other redox-sensitive metal/radionuclide contaminants that were released to the environment in large quantities during Cold War nuclear weapons manufacturing operations. Several fundamental scientific questions were addressed in order to understand and predict how such treatment procedures would function under in situ conditions in the subsurface. These questions revolved the coupled microbial-geochemical phenomena which are likely to occur within a redox barrier treatment zone, and on the dynamic interactions between hydrologic flux and biogeochemical process rates. First, we assembled a robust conceptual understanding and numerical framework for modeling the kinetics of microbial Fe(III) oxide reduction and associated DMRB growth in sediments. Development of this framework is a critical prerequisite for predicting the potential effectiveness of DMRB-promoted subsurface bioremediation, since Fe(III) oxides are expected to be the primary source of electron-accepting capacity for growth and maintenance of DMRB in subsurface environments. We also defined in detail the kinetics of microbial (enzymatic) versus abiotic, ferrous iron-promoted reduction of U(VI) in the presence and absence of synthetic and natural Fe(III) oxide materials. The results of these studies suggest that (i) the efficiency of dissolved U(VI) scavenging may be influenced by the kinetics of enzymatic U(VI) reduction in systems with relative short fluid residence times; (2) association of U(VI) with diverse surface sites in natural soils and sediments has the potential to limit the rate and extent of microbial U(VI) reduction, and in turn modulate the effectiveness of in situ U(VI) bioremediation; and (3) abiotic, ferrous iron (Fe(II)) drive n U
Non-sensitized selective photochemical reduction of CO2 to CO under visible light with an iron molecular catalyst.
Rao, Heng; Bonin, Julien; Robert, Marc
A substituted tetraphenyl iron porphyrin, bearing positively charged trimethylammonio groups at the para position of each phenyl ring, demonstrates its ability as a homogeneous molecular catalyst to selectively reduce CO 2 to CO under visible light irradiation in organic media without the assistance of a sensitizer and no competitive hydrogen evolution for several days.
Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy
Energy Technology Data Exchange (ETDEWEB)
Fan, Jian-Xin [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); School of River and Ocean Engineering, Chongqing Jiaotong University, Chongqing 400074 (China); Wang, Yu-Jun, E-mail: email@example.com [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Liu, Cun [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Wang, Li-Hua; Yang, Ke [Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of sciences, Shanghai 201204 (China); Zhou, Dong-Mei, E-mail: firstname.lastname@example.com [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Li, Wei; Sparks, Donald L. [Environmental Soil Chemistry Group, Delaware Environmental Institute and Department of Plant and Soil Sciences, University of Delaware, Newark, DE 19717-1303 United States (United States)
Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils.
Effect of iron oxide reductive dissolution on the transformation and immobilization of arsenic in soils: New insights from X-ray photoelectron and X-ray absorption spectroscopy
International Nuclear Information System (INIS)
Fan, Jian-Xin; Wang, Yu-Jun; Liu, Cun; Wang, Li-Hua; Yang, Ke; Zhou, Dong-Mei; Li, Wei; Sparks, Donald L.
Graphical abstract: - Highlights: • Immobility and transformation of As on different Eh soils were investigated. • μ-XRF, XANES, and XPS were used to gain As distribution and speciation in soil. • Sorption capacity of As on anaerobic soil was much higher than that on oxic soil. • Fe oxides reductive dissolution is a key factor for As sorption and transformation. - Abstract: The geochemical behavior and speciation of arsenic (As) in paddy soils is strongly controlled by soil redox conditions and the sequestration by soil iron oxyhydroxides. Hence, the effects of iron oxide reductive dissolution on the adsorption, transformation and precipitation of As(III) and As(V) in soils were investigated using batch experiments and synchrotron based techniques to gain a deeper understanding at both macroscopic and microscopic scales. The results of batch sorption experiments revealed that the sorption capacity of As(V) on anoxic soil was much higher than that on control soil. Synchrotron based X-ray fluorescence (μ-XRF) mapping studies indicated that As was heterogeneously distributed and was mainly associated with iron in the soil. X-ray absorption near edge structure (XANES), micro-X-ray absorption near edge structure (μ-XANES) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the primary speciation of As in the soil is As(V). These results further suggested that, when As(V) was introduced into the anoxic soil, the rapid coprecipitation of As(V) with ferric/ferrous ion prevented its reduction to As(III), and was the main mechanism controlling the immobilization of As. This research could improve the current understanding of soil As chemistry in paddy and wetland soils
Effect of Amount of Carbon on the Reduction Efficiency of Iron Ore-Coal Composite Pellets in Multi-layer Bed Rotary Hearth Furnace (RHF)
Mishra, Srinibash; Roy, Gour Gopal
The effect of carbon-to-hematite molar ratio has been studied on the reduction efficiency of iron ore-coal composite pellet reduced at 1523 K (1250 °C) for 20 minutes in a laboratory scale multi-layer bed rotary hearth furnace (RHF). Reduced pellets have been characterized through weight loss measurement, estimation of porosity, shrinkage, qualitative and quantitative phase analysis by XRD. Performance parameters such as the degree of reduction, metallization, carbon efficiency, productivity, and compressive strength have been calculated to compare the process efficacy at different carbon levels in the pellets. Pellets with optimum carbon-to-hematite ratio (C/Fe2O3 molar ratio = 1.66) that is much below the stoichiometric carbon required for direct reduction of hematite yielded maximum reduction, better carbon utilization, and productivity for all three layers. Top layer exhibited maximum reduction at comparatively lower carbon level (C/Fe2O3 molar ratio 2.33). Correlation between degree of reduction and metallization indicated non-isothermal kinetics influenced by heat and mass transfer in multi-layer bed RHF. Compressive strength of the partially reduced pellet with optimum carbon content (C/Fe2O3 molar ratio = 1.66) showed that they could be potentially used as an alternate feed in a blast furnace or any other smelting reactor.
Long distance electron transmission in marine sediment
DEFF Research Database (Denmark)
Risgaard-Petersen, Nils; Nielsen, Lars Peter
processes leads to formation of electrical fields, which modifies ion transport. The local proton producing and proton consuming half reactions induces pH extremes that accelerate dissolution of iron sul-phides and calcium carbonates in anoxic layers and promotes the formation of Mg-calcite and iron oxides......Geochemical observations in marine sediment have recently shown that electric currents may intimately couple spatially separated biogeochemical processes like oxygen reduction at the sediment surface and hydrogen sul-phide oxidation in anoxic layers centimeters below 1. Further experimental studies...... suggest that the electron conductance is mediated by microorgan-isms. The spatial separation of electron and proton donors and acceptors has major impacts on element cycling by redox processes, pH balances, mineral dissolution/precipitations, and electromigration of ions. The sepa-ration of redox...
Alkaline Fe(III) reduction by a novel alkali-tolerant Serratia sp. isolated from surface sediments close to Sellafield nuclear facility, UK.
Thorpe, Clare L; Morris, Katherine; Boothman, Christopher; Lloyd, Jonathan R
Extensive denitrification resulted in a dramatic increase in pH (from 6.8 to 9.5) in nitrate-impacted, acetate-amended sediment microcosms containing sediment representative of the Sellafield nuclear facility, UK. Denitrification was followed by Fe(III) reduction, indicating the presence of alkali-tolerant, metal-reducing bacteria. A close relative (99% 16S rRNA gene sequence homology) to Serratia liquefaciens dominated progressive enrichment cultures containing Fe(III)-citrate as the sole electron acceptor at pH 9 and was isolated aerobically using solid media. The optimum growth conditions for this facultatively anaerobic Serratia species were investigated, and it was capable of metabolizing a wide range of electron acceptors including oxygen, nitrate, FeGel, Fe-NTA and Fe-citrate and electron donors including acetate, lactate, formate, ethanol, glucose, glycerol and yeast extract at an optimum pH of c. 6.5 at 20 °C. The alkali tolerance of this strain extends the pH range of highly adaptable Fe(III)-reducing Serratia species from mildly acidic pH values associated with acid mine drainage conditions to alkali conditions representative of subsurface sediments stimulated for extensive denitrification and metal reduction. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.
Acidithrix ferrooxidans gen. nov., sp. nov.; a filamentous and obligately heterotrophic, acidophilic member of the Actinobacteria that catalyzes dissimilatory oxido-reduction of iron.
Jones, Rose M; Johnson, D Barrie
A novel acidophilic member of the phylum Actinobacteria was isolated from an acidic stream draining an abandoned copper mine in north Wales. The isolate (PY-F3) was demonstrated to be a heterotroph that catalyzed the oxidation of ferrous iron (but not of sulfur or hydrogen) under aerobic conditions, and the reduction of ferric iron under micro-aerobic and anaerobic conditions. PY-F3 formed long entangled filaments of cells (>50 μm long) during active growth phases, though these degenerated into smaller fragments and single cells in late stationary phase. Although isolate PY-F3 was not observed to grow below pH 2.0 and 10 °C, harvested biomass was found to oxidize ferrous iron at relatively fast rates at pH 1.5 and 5 °C. Phylogenetic analysis, based on comparisons of 16S rRNA gene sequences, showed that isolate PY-F3 has 91-93% gene similarity to those of the four classified genera and species of acidophilic Actinobacteria, and therefore is a representative of a novel genus. The binomial Acidithrix ferrooxidans is proposed for this new species, with PY-F3 as the designated type strain (=DSM 28176(T), =JCM 19728(T)). Copyright © 2015 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.
The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...
Twenty two years of sewage sludge marine disposal monitoring in the Eastern Mediterranean Sea: Impact on sediment quality and infauna and the response to load reduction.
Kress, N; Shoham-Frider, E; Galil, B S
Effects of sewage sludge disposal on sediments and infauna are presented in a unique long-term (22years) data set from the Eastern Mediterranean. While organic carbon (Corg) and metals affected sediment quality in an area which size varied seasonally, the infauna exhibited seasonal "boom and bust" cycle. Metal concentrations declined following load reduction. However, Corg did not decrease and infaunal abundance, closely related to Corg, varied with changes in environmental forcing. Mild winters affected the infaunal populations at the heavily impacted stations, due to anoxic conditions. Planned cessation of disposal is estimated to reduce Corg and metal concentrations to pre-discharge levels. Yet the resettling biota is expected to differ significantly from the pre-discharge one and consist in large part of Erythraean non indigenous species. Copyright © 2016 Elsevier Ltd. All rights reserved.
Iron isotope biogeochemistry of Neoproterozoic marine shales
Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.
Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size
Reduction-induced inward diffusion and crystal growth on the surfaces of iron-bearing silicate glasses
DEFF Research Database (Denmark)
Liu, S.J.; Tao, H.Z.; Zhang, Y.F.
We investigate the sodium inward diffusion (i.e., sodium diffusion from surface toward interior) in iron containing alkaline earth silicate glasses under reducing conditions around Tg and the induced surface crystallization. The surface crystallization is caused by formation of a silicate-gel lay......+ ions have stronger bonds to oxygen and lower coordination number (4~5) than Ca2+, Sr2+ and Ba2+ ions. In contrast, a cristobalite layer forms in Ca-, Sr- and Ba-containing glasses....
Utilization of subsurface microbial electrochemical systems to elucidate the mechanisms of competition between methanogenesis and microbial iron(III)/humic acid reduction in Arctic peat soils
Friedman, E. S.; Miller, K.; Lipson, D.; Angenent, L. T.
High-latitude peat soils are a major carbon reservoir, and there is growing concern that previously dormant carbon from this reservoir could be released to the atmosphere as a result of continued climate change. Microbial processes, such as methanogenesis and carbon dioxide production via iron(III) or humic acid reduction, are at the heart of the carbon cycle in Arctic peat soils [1]. A deeper understanding of the factors governing microbial dominance in these soils is crucial for predicting the effects of continued climate change. In previous years, we have demonstrated the viability of a potentiostatically-controlled subsurface microbial electrochemical system-based biosensor that measures microbial respiration via exocellular electron transfer [2]. This system utilizes a graphite working electrode poised at 0.1 V NHE to mimic ferric iron and humic acid compounds. Microbes that would normally utilize these compounds as electron acceptors donate electrons to the electrode instead. The resulting current is a measure of microbial respiration with the electrode and is recorded with respect to time. Here, we examine the mechanistic relationship between methanogenesis and iron(III)- or humic acid-reduction by using these same microbial-three electrode systems to provide an inexhaustible source of alternate electron acceptor to microbes in these soils. Chamber-based carbon dioxide and methane fluxes were measured from soil collars with and without microbial three-electrode systems over a period of four weeks. In addition, in some collars we simulated increased fermentation by applying acetate treatments to understand possible effects of continued climate change on microbial processes in these carbon-rich soils. The results from this work aim to increase our fundamental understanding of competition between electron acceptors, and will provide valuable data for climate modeling scenarios. 1. Lipson, D.A., et al., Reduction of iron (III) and humic substances plays a major
Using learning curves on energy-efficient technologies to estimate future energy savings and emission reduction potentials in the U.S. iron and steel industry
Energy Technology Data Exchange (ETDEWEB)
Karali, Nihan [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Park, Won Young [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); McNeil, Michael A. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Increasing concerns on non-sustainable energy use and climate change spur a growing research interest in energy efficiency potentials in various critical areas such as industrial production. This paper focuses on learning curve aspects of energy efficiency measures in the U.S iron and steel sector. A number of early-stage efficient technologies (i.e., emerging or demonstration technologies) are technically feasible and have the potential to make a significant contribution to energy saving and CO2 emissions reduction, but fall short economically to be included. However, they may also have the cost effective potential for significant cost reduction and/or performance improvement in the future under learning effects such as 'learning-by-doing'. The investigation is carried out using ISEEM, a technology oriented, linear optimization model. We investigated how steel demand is balanced with/without the availability learning curve, compared to a Reference scenario. The retrofit (or investment in some cases) costs of energy efficient technologies decline in the scenario where learning curve is applied. The analysis also addresses market penetration of energy efficient technologies, energy saving, and CO2 emissions in the U.S. iron and steel sector with/without learning impact. Accordingly, the study helps those who use energy models better manage the price barriers preventing unrealistic diffusion of energy-efficiency technologies, better understand the market and learning system involved, predict future achievable learning rates more accurately, and project future savings via energy-efficiency technologies with presence of learning. We conclude from our analysis that, most of the existing energy efficiency technologies that are currently used in the U.S. iron and steel sector are cost effective. Penetration levels increases through the years, even though there is no price reduction. However, demonstration technologies are not economically
Remobilisation of uranium from contaminated freshwater sediments by bioturbation
Energy Technology Data Exchange (ETDEWEB)
Lagauzere, S.; Bonzom, J.M. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Saint-Paul-Lez-Durance (France). Lab. d' Ecotoxicologie des Radionucleides; Motelica-Heino, M. [Orleans Univ. (France). ISTO; Viollier, E. [Paris Diderot Univ., Paris (France). Inst. de Physique du Globe de Paris; Stora, G. [Aix-Marseille Univ., Marseille (France). Mediterranean Inst. of Oceanography (MIO)
Benthic macro-invertebrate bioturbation can influence the remobilisation of uranium (U) initially associated with freshwater sediments, resulting in a high release of this pollutant through the overlying water column. Given the potential negative effects on aquatic biocenosis and the global ecological risk, it appears crucial to improve our current knowledge concerning the biogeochemical behaviour of U in sediments. The present study aimed to assess the biogeochemical modifications induced by Tubifex tubifex (Annelida, Clitellata, Tubificidae) bioturbation within the sediment in order to explain such a release of U. To reach this goal, U distribution between solid and solute phases of a reconstructed benthic system (i.e. in mesocosms) inhabited or not by T. tubifex worms was assessed in a 12-day laboratory experiment. Thanks notably to fine-resolution (mm-scale) measurements (e.g. ''diffusive equilibrium in thin-films'' DET gel probes for porewater, bioaccumulation in worms) of U and main chemical species (iron, sulfate, nitrate and nitrite), this work (i) confirmed that the removal of bottom sediment particles to the surface through the digestive tract of worms greatly favoured oxidative loss of U in the water column, and (ii) demonstrated that both U contamination and bioturbation of T. tubifex substantially influenced major microbial-driven biogeochemical reactions in sediments (e.g. stimulation of denitrification, sulfate reduction and iron dissolutive reduction). This study provides the first demonstration of biogeochemical modifications induced by bioturbation in freshwater U-contaminated sediments.
Reduction of hexavalent chromium by ferrous iron: A process of chromium isotope fractionation and its relevance to natural environments
DEFF Research Database (Denmark)
Døssing, Lasse Nørbye; Dideriksen, Knud; Stipp, Susan Louise Svane
Stable chromium (Cr) isotopes can be used as a tracer for changing redox conditions in modern marine systems and in the geological record. We have investigated isotope fractionation during reduction of Cr(VI)aq by Fe(II)aq. Reduction of Cr(VI)aq by Fe(II)aq in batch experiments leads to significant...
Modelling CEC variations versus structural iron reduction levels in dioctahedral smectites. Existing approaches, new data and model refinements.
Hadi, Jebril; Tournassat, Christophe; Ignatiadis, Ioannis; Greneche, Jean Marc; Charlet, Laurent
A model was developed to describe how the 2:1 layer excess negative charge induced by the reduction of Fe(III) to Fe(II) by sodium dithionite buffered with citrate-bicarbonate is balanced and applied to nontronites. This model is based on new experimental data and extends structural interpretation introduced by a former model [36-38]. The 2:1 layer negative charge increase due to Fe(III) to Fe(II) reduction is balanced by an excess adsorption of cations in the clay interlayers and a specific sorption of H(+) from solution. Prevalence of one compensating mechanism over the other is related to the growing lattice distortion induced by structural Fe(III) reduction. At low reduction levels, cation adsorption dominates and some of the incorporated protons react with structural OH groups, leading to a dehydroxylation of the structure. Starting from a moderate reduction level, other structural changes occur, leading to a reorganisation of the octahedral and tetrahedral lattice: migration or release of cations, intense dehydroxylation and bonding of protons to undersaturated oxygen atoms. Experimental data highlight some particular properties of ferruginous smectites regarding chemical reduction. Contrary to previous assumptions, the negative layer charge of nontronites does not only increase towards a plateau value upon reduction. A peak is observed in the reduction domain. After this peak, the negative layer charge decreases upon extended reduction (>30%). The decrease is so dramatic that the layer charge of highly reduced nontronites can fall below that of its fully oxidised counterpart. Furthermore, the presence of a large amount of tetrahedral Fe seems to promote intense clay structural changes and Fe reducibility. Our newly acquired data clearly show that models currently available in the literature cannot be applied to the whole reduction range of clay structural Fe. Moreover, changes in the model normalising procedure clearly demonstrate that the investigated low
Synthesis of novel magnetic iron metal-silica (Fe-SBA-15) and magnetite-silica (Fe{sub 3}O{sub 4}-SBA-15) nanocomposites with a high iron content using temperature-programed reduction
Energy Technology Data Exchange (ETDEWEB)
Yiu, H H P [Department of Chemistry, University of Liverpool, Liverpool, Merseyside L69 7ZD (United Kingdom); Keane, M A [Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Lethbridge, Z A D [Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL (United Kingdom); Lees, M R [Department of Physics, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL (United Kingdom); Haj, A J El; Dobson, J [Institute of Science and Technology in Medicine, Keele University, Thornburrow Drive, Hartshill, Stoke-on-Trent ST4 7QB (United Kingdom)], E-mail: firstname.lastname@example.com
Magnetic iron metal-silica and magnetite-silica nanocomposites have been prepared via temperature-programed reduction (TPR) of an iron oxide-SBA-15 (SBA: Santa Barbara Amorphous) composite. TPR of the starting SBA-15 supported Fe{sub 2}O{sub 3} generated Fe{sub 3}O{sub 4} and FeO as stepwise intermediates in the ultimate formation of Fe-SBA-15. The composite materials have been characterized by means of x-ray diffraction, high resolution transmission electron microscopy and SQUID (superconducting quantum interference device) magnetometry. The Fe oxide and metal components form a core, as nanoscale particles, that is entrapped in the SBA-15 pore network. Fe{sub 3}O{sub 4}-SBA-15 and Fe-SBA-15 exhibited superparamagnetic properties with a total magnetization value of 17 emu g{sup -1}. The magnetite-silica composite (at an Fe{sub 3}O{sub 4} loading of 30% w/w) delivered a magnetization that exceeded values reported in the literature or obtained with commercial samples. Due to the high pore volume of the mesoporous template, the magnetite content can be increased to 83% w/w with a further enhancement of magnetization.
Temperature dependence of microbial degradation of organic matter in marine sediments: polysaccharide hydrolysis, oxygen consumption, and sulfate reduction
DEFF Research Database (Denmark)
Arnosti, C.; Jørgensen, BB; Sagemann, J.
temperatures, optimum temperatures generally decreased with decreasing environmental temperatures. Activity at 5 degrees C as a percentage of highest activity was highest in the Arctic sites and lowest in the warmest temperate site. The highest potential rates of substrate hydrolysis were measured...... suggest that organic carbon turnover in the cold Arctic is not intrinsically slower than carbon turnover in temperate environments; sedimentary metabolism in Arctic sediments may be controlled more by organic matter supply than by temperature.......The temperature dependence of representative initial and terminal steps of organic carbon remineralization was measured at 2 temperate sites with annual temperature ranges of 0 to 30 degrees C and 4 to 15 degrees C and 2 Arctic sites with temperatures of 2.6 and -1.7 degrees C. Slurried sediments...
Radium desorption, manganese and iron dissolution from sand filters of a conventional ground water treatment plant under reductive conditions
International Nuclear Information System (INIS)
Al-Hobaib, A.S.; Al-Sulaiman, K.M.; Al-Dhayan, D.M.; Al-Suhybani, A.A.
Sand filters are used as a filter bed in many ground water treatment plants to remove the physical contaminants and oxidation products. A build-up of radioactivity may take place on the granules, where iron and manganese oxides are deposited and form thin films on the surface of sand filter. The oxides of iron and manganese play an important role in adsorbing radium from ground water. The disposal of those granules makes a significant problem. A batch technique is used for solubilization of radium from sand filters in the presence of some organic acids, which act as reducing agents. These acids are formic acid, acetic acid, benzoic acid, succinic acid, oxalic acid, phthalic acid, and adipic acid. The data were obtained as a function of acidity, temperature, contact time and liquid/solid ratio particle size and shaking speed. It was found that oxalic acid was the best for radium removal. The effectiveness of these acids on radium removal was as follows: oxalic acid > phthalic acid > adipic acid > succinic acid > formic acid > acetic acid. The maximum removal obtained was 69.9% at 1M oxalic acid at 8 ml/g ratio. Reaction kinetics and mechanism parameters of the dissolution process were studied and compared with other published data. (author)
Electrochemical CO2 Reduction by Ni-containing Iron Sulfides: How Is CO2 Electrochemically Reduced at Bisulfide-Bearing Deep-sea Hydrothermal Precipitates?
International Nuclear Information System (INIS)
Yamaguchi, Akira; Yamamoto, Masahiro; Takai, Ken; Ishii, Takumi; Hashimoto, Kazuhito; Nakamura, Ryuhei
The discovery of deep-sea hydrothermal vents on the late 1970's has led to many hypotheses concerning chemical evolution in the prebiotic ocean and the early evolution of energy metabolism in ancient Earth. Such studies stand on the quest for the bioenergetic evolution to utilize reducing chemicals such as H 2 for CO 2 reduction and carbon assimilation. In addition to the direct reaction of H 2 and CO 2 , the electrical current passing across a bisulfide-bearing chimney structure has pointed to the possible electrocatalytic CO 2 reduction at the cold ocean-vent interface (R. Nakamura, et al. Angew. Chem. Int. Ed. 2010, 49, 7692 − 7694). To confirm the validity of this hypothesis, here, we examined the energetics of electrocatalytic CO 2 reduction by iron sulfide (FeS) deposits at slightly acidic pH. Although FeS deposits inefficiently reduced CO 2 , the efficiency of the reaction was substantially improved by the substitution of Fe with Ni to form FeNi 2 S 4 (violarite), of which surface was further modified with amine compounds. The potential-dependent activity of CO 2 reduction demonstrated that CO 2 reduction by H 2 in hydrothermal fluids was involved in a strong endergonic electron transfer reaction, suggesting that a naturally occurring proton-motive force (PMF) as high as 200 mV would be established across the hydrothermal vent chimney wall. However, in the chimney structures, H 2 generation competes with CO 2 reduction for electrical current, resulting in rapid consumption of the PMF. Therefore, to maintain the PMF and the electrosynthesis of organic compounds in hydrothermal vent mineral deposits, we propose a homeostatic pH regulation mechanism of FeS deposits, in which elemental hydrogen stored in the hydrothermal mineral deposits is used to balance the consumption of the electrochemical gradient by H 2 generation
Monitoring and evaluation of plant and hydrological controls on arsenic transport across the water sediment interface
Jaffe, P. R.; MacDonald, L. H.; Paull, J.
Plants and hydrology influence the transport of arsenic in wetlands by changing the dominant redox chemistry in the subsurface, and different plant and hydrological regimes can serve as effective barriers or promoters of metal transport. Inorganic arsenic, especially arsenate, binds to iron oxides in wetlands. In flooded wetland sediments, organic carbon from plants consumes oxygen and promotes reductive iron dissolution, which leads to arsenic release, while plants simultaneously create microoxic regimes around root hairs that oxidize and precipitate iron, promoting arsenic capture. Hydrology influences arsenic mobility by promoting wetting and drying cycles. Such cycles can lead to rapid shifts from anaerobic to aerobic conditions, and vice versa, with lasting impact on the oxidation state of iron and, by extension, the mobility of arsenic. Remediation strategies should take these competing conditions into account, and to help inform these strategies this study examines the chemistry of an industrially contaminated wetland when the above mechanisms aggregate. The study tests whether, in bulk, plants promote iron reduction or oxidation in intermittently flooded or consistently flooded sediments, and how this impacts arsenic mobility. This research uses a novel dialysis-based monitoring technique to examine the macro-properties of arsenic transport at the sediment water interface and at depth. Dialysis-based monitoring allows long-term seasonal trends in anaerobic porewater and allows active hypothesis testing on the influence of plants on redox chemistry. This study finds that plants promote iron reduction and that iron-reducing zones tend to correlate with zones with mobile arsenic. However, one newly reported and important finding of this study is that a brief summer drought that dried and oxidized sediments with a long history of iron-reduction zone served to effectively halt iron reduction for many months, and this corresponded to a lasting decline in
Solid-solution partitioning and thionation of diphenylarsinic acid in a flooded soil under the impact of sulfate and iron reduction
Energy Technology Data Exchange (ETDEWEB)
Zhu, Meng [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tu, Chen [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Hu, Xuefeng; Zhang, Haibo [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Lijuan [Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800 (China); Wei, Jing [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Li, Yuan [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Luo, Yongming, E-mail: firstname.lastname@example.com [Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003 (China); Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Christie, Peter [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)
DPAA. - Highlights: • We first investigated the solid-solution partitioning of DPAA in a flooded soil. • We first examined the impacts of sulfate and iron reduction on DPAA partitioning. • Elevated DPAA mobilization and thionation was observed in sulfide soil. • DPAA mobilization associated with Fe(III) reductive dissolution was demonstrated. • Enhanced mobilization of DPAA and sulfate reduction promoted DPAA thionation.
Study on energy saving and the CO{sub 2} reduction plan of Korean iron and steel industry
Energy Technology Data Exchange (ETDEWEB)
Kim, J.W.; Kim, J.I.; Kim, S.R. [Korea Energy Economics Institute, Euiwang (Korea, Republic of)
An iron and steel company which consumes a lot of energy should continue restructuring with integrated management methods based on a thorough profitability principle together with continuous investment in green technology development, and actively search for advancing plans to upper and lower streams through vigorous foreign investment. The iron and steel industry now must realize that environmental strategy will eventually be converted into the profit of the company eventually, and escape from the reactive attitude of the past on environment. It is urgently required that they possess an aggressive management strategy that could capture the impact of environmental regulation which may be far greater than the Uruguay Round (UR) of the past as the opportunistic factor that would rather increase the power of the company. Now enterprises need a change of attitude that handles the capital invested in environment as an aggressive strategic element that could guarantee the profit for the future not as mere concept of expenses. As in the case of the 3M company, the concept of `Polluter Pays Principle` should be accepted as the 3P concept of pollution- prevention compensation principle called as the concept of `Pollution Prevention Pays`. That is, expanding the use of clean energy and raising the public image as an environment-friendly enterprise has become an important assignment of an entrepreneur now. First of all, all employees including top management must renew their recognition on environmental management. They should be able to have collective wisdom enough to take advantage of the manpower and resources required for minimizing environmental damages as the investment or opportunistic element that could bring tangible and intangible profits in the future. 33 refs., 2 figs., 11 tabs.
The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?
Balind, K.; Barber, A.; Gélinas, Y.
The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.
Iron oxide minerals in dust-source sediments from the Bodélé Depression, Chad: Implications for radiative properties and Fe bioavailability of dust plumes from the Sahara
Moskowitz, Bruce M; Reynolds, Richard L.; Goldstein, Harland L.; Beroquo, Thelma; Kokaly, Raymond F.; Bristow, Charlie S
Atmospheric mineral dust can influence climate and biogeochemical cycles. An important component of mineral dust is ferric oxide minerals (hematite and goethite) which have been shown to influence strongly the optical properties of dust plumes and thus affect the radiative forcing of global dust. Here we report on the iron mineralogy of dust-source samples from the Bodélé Depression (Chad, north-central Africa), which is estimated to be Earth's most prolific dust producer and may be a key contributor to the global radiative budget of the atmosphere as well as to long-range nutrient transport to the Amazon Basin. By using a combination of magnetic property measurements, Mössbauer spectroscopy, reflectance spectroscopy, chemical analysis, and scanning electron microscopy, we document the abundance and relative amounts of goethite, hematite, and magnetite in dust-source samples from the Bodélé Depression. The partition between hematite and goethite is important to know to improve models for the radiative effects of ferric oxide minerals in mineral dust aerosols. The combination of methods shows (1) the dominance of goethite over hematite in the source sediments, (2) the abundance and occurrences of their nanosize components, and (3) the ubiquity of magnetite, albeit in small amounts. Dominant goethite and subordinate hematite together compose about 2% of yellow-reddish dust-source sediments from the Bodélé Depression and contribute strongly to diminution of reflectance in bulk samples. These observations imply that dust plumes from the Bodélé Depression that are derived from goethite-dominated sediments strongly absorb solar radiation. The presence of ubiquitous magnetite (0.002–0.57 wt%) is also noteworthy for its potentially higher solubility relative to ferric oxide and for its small sizes, including PM iron apportionment is estimated at about 33% in ferric oxide minerals, 1.4% in magnetite, and 65% in ferric silicates. Structural iron in clay
High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor
Energy Technology Data Exchange (ETDEWEB)
Song, Ping; Barkholtz, Heather M.; Wang, Ying; Xu, Weilin; Liu, Dijia; Zhuang, Lin
We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives of Pt-based catalysts with best performance/price.
Directory of Open Access Journals (Sweden)
Jean C. Cruz
Full Text Available This study investigated the reductive degradation of acetamiprid (5 mg L-1 in aqueous medium (at pH 2.0 induced by zero-valent iron (50 mg. The process was monitored using high-performance liquid chromatography (HPLC to determine the degradation rate as a function of reaction time, and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS to search for (and potentially characterize any possible byproducts formed during degradation. The results obtained via HPLC showed that after 60 min, the degradation of the substrate reached nearly 100% in an acidic medium, whereas the mineralization rate (as determined by total organic carbon measurements was as low as 3%. Data obtained by DI-ESI-MS showed that byproducts were formed mainly by insertions of hydrogen atoms into the nitrile, imine, and pyridine ring moieties, in addition to the observation of chlorine substitution by hydrogen replacement (hydrodechlorination reactions.
Iron(II) phthalocyanine covalently functionalized graphene as a highly efficient non-precious-metal catalyst for the oxygen reduction reaction in alkaline media
International Nuclear Information System (INIS)
Liu, Ying; Wu, Yan-Ying; Lv, Guo-Jun; Pu, Tao; He, Xing-Quan; Cui, Li-Li
Graphical abstract: The fabricated FePc-Gr catalyst for ORR exhibited high activity, favoring a direct 4-electron process, good stability and selectivity, all of which should be attributed to its high conductivity, the synergistic effect between FePc and graphene, as well as the formation of stable FePc-Gr composite through covalent bonding and π–π interaction. - Abstract: A novel iron(II) phthalocyanine covalently modified graphene (FePc-Gr) was synthesized by reduction of the product obtained through an amidation reaction between carboxyl-functionalized graphene oxide (CFGO) and iron(II) tetra-aminophthalocyanine (FeTAPc). The FePc-Gr hybird was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrocatalytic properties of FePc-Gr toward the oxygen reduction reaction (ORR) were evaluated using cyclic voltammetry (CV) and linear sweep voltammetry methods. The peak potential of the ORR on the FePc-Gr catalyst was found to be about −0.12 V vs. SCE in 0.1 M NaOH solution, which was 180 and 360 mV more positive than that on FeTAPc and bare GCE, respectively. The rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) measurements revealed that the ORR mechanism was nearly via a direct four-electron pathway to water on FePc-Gr. The current still remained 83.5% of its initial after chronoamperometric test for 10,000 s. Nevertheless, Pt/C catalyst only retained 40.5% of its initial current. The peak potential and peak current changed slightly when 3 M methanol was introduced. So the FePc-Gr composite catalyst for ORR exhibited high activity, good stability and methanol-tolerance, which could be used as a promising Pt-free catalyst for ORR in alkaline direct methanol fuel cell (DMFC)
Radiotracer Imaging of Sediment Columns
Moses, W. W.; O'Neil, J. P.; Boutchko, R.; Nico, P. S.; Druhan, J. L.; Vandehey, N. T.
Nuclear medical PET and SPECT cameras routinely image radioactivity concentration of gamma ray emitting isotopes (PET - 511 keV; SPECT - 75-300 keV). We have used nuclear medical imaging technology to study contaminant transport in sediment columns. Specifically, we use Tc-99m (T1/2 = 6 h, Eγ = 140 keV) and a SPECT camera to image the bacteria mediated reduction of pertechnetate, [Tc(VII)O4]- + Fe(II) → Tc(IV)O2 + Fe(III). A 45 mL bolus of Tc-99m (32 mCi) labeled sodium pertechnetate was infused into a column (35cm x 10cm Ø) containing uranium-contaminated subsurface sediment from the Rifle, CO site. A flow rate of 1.25 ml/min of artificial groundwater was maintained in the column. Using a GE Millennium VG camera, we imaged the column for 12 hours, acquiring 44 frames. As the microbes in the sediment were inactive, we expected most of the iron to be Fe(III). The images were consistent with this hypothesis, and the Tc-99m pertechnetate acted like a conservative tracer. Virtually no binding of the Tc-99m was observed, and while the bolus of activity propagated fairly uniformly through the column, some inhomogeneity attributed to sediment packing was observed. We expect that after augmentation by acetate, the bacteria will metabolically reduce Fe(III) to Fe(II), leading to significant Tc-99m binding. Imaging sediment columns using nuclear medicine techniques has many attractive features. Trace quantities of the radiolabeled compounds are used (micro- to nano- molar) and the half-lives of many of these tracers are short (Image of Tc-99m distribution in a column containing Rifle sediment at four times.
Evaporated self-supporting foils of enriched iron from the in-situ reduction of Fe2O3
International Nuclear Information System (INIS)
Riel, W.D.
This paper describes the reduction of isotopically enriched Fe 2 O 3 usng a controlled thermite reaction. The method will produce strain free evaporated films of 100-300 μg/cm 2 which can be floated and mounted, using standard techniques, to make strong self-supporting targets. (author)
Heterogeneous electron transfer and oxygen reduction reaction at nanostructured iron(II) phthalocyanine and its MWCNTs nanocomposites
CSIR Research Space (South Africa)
Mamuru, SA
Full Text Available species within the porous layers of MWCNTs. Electron transfer process is much easier at the EPPGE-MWCNT and EPPGE-MWCNT-nanoFePc compared to the other electrodes. The best response for oxygen reduction reaction was at the EPPGE-MWCNTnanoFePc, yielding a 4...
Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars
Catling, David; Moore, Jeff
Iron formations are ancient, laminated chemical sediments containing at least 15 wt% Fe. We discuss possible mechanisms for their formation in aqueous environments on early Mars. Such iron oxide deposits may be detectable today.
Fe-C-S systematics in Bengal Fan sediments
Volvoikar, S. P.; Mazumdar, A.; Goswami, H.; Pujari, S.; Peketi, A.
Global biogeochemical cycles of iron, carbon and sulfur (Fe-C-S) are interrelated. Sulfate reduction in marine sediments is the major factor controlling the cycling and burial of carbon, sulfur and iron. Organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) are the two main processes responsible for sulfate reduction in marine sediments. The amount and reactivity of organic matter, iron minerals and concentrations of dissolved sulfide in pore water control the burial of iron sulfide and organic bound sulfur in marine sediments. Here we investigate the sulfidization process in a sediment core from the western part of upper Bay of Bengal fan characterized by efficient burial of organic matter with siliclastic load. A 30 m long sediment core (MD 161/29, Lat. 170 18.04' N, Long. 870 22.56' E, water depth: 2434m) was collected onboard Marion Dufresne (May, 2007) and studied for Fe-S speciation and organic matter characterization. Buffered dithionite extractable iron (FeD) varies from 0.71 to 1.43 wt % (Avg. 0.79 wt %). FeD represents Fe oxides and oxyhydroxides mainly, ferrihydrite, lepidocrocite, goethite and hematite. Acid volatile sulfur (AVS) varies from 0.0015 to 0.63 wt % (avg: 0.058 wt %), while chromium reducible sulfur (CRS) varies from 0.00047 to 0.29 wt % (avg. 0.054 wt %). Based on the vertical distribution patterns of FeD, AVS and CRS, the core is divided into three zones, the lower (3000 to 1833 cm), middle (1833 to 398 cm) and upper (398 cm to surface) zones. FeD shows higher concentration in the lower zone. FeTR (FeOx + FeD + FeCRS + FeAVS) also exhibit higher concentration in this zone, suggesting higher availability of reactive iron for iron sulfide precipitation. AVS, elemental sulfur, spikes of CRS and gradual enrichment of δ34SAVS and δ34SCRS with sharp peaks in-between is noted in the lower zone. The gradual enrichment of δ34SAVS and δ34SCRS is the outcome of late diagenetic pyritization with higher availability of sulfide
Reduction experiment of FeO-bearing amorphous silicate: application to origin of metallic iron in GEMS
Energy Technology Data Exchange (ETDEWEB)
Matsuno, Junya; Tsuchiyama, Akira; Miyake, Akira [Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwake, Sakyo-ku, Kyoto 606-8502 (Japan); Noguchi, Ryo [Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan); Ichikawa, Satoshi, E-mail: firstname.lastname@example.com [Institute for Nano-science Design, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)
Glass with embedded metal and sulfides (GEMS) are amorphous silicates included in anhydrous interplanetary dust particles (IDPs) and can provide information about material evolution in our early solar system. Several formation processes for GEMS have been proposed so far, but these theories are still being debated. To investigate a possible GEMS origin by reduction of interstellar silicates, we synthesized amorphous silicates with a mean GEMS composition and performed heating experiments in a reducing atmosphere. FeO-bearing amorphous silicates were heated at 923 K and 973 K for 3 hr, and at 1023 K for 1-48 hr at ambient pressure in a reducing atmosphere. Fe grains formed at the interface between the silicate and the reducing gas through a reduction. In contrast, TEM observations of natural GEMS show that metallic grains are uniformly embedded in amorphous silicates. Therefore, the present study suggests that metallic inclusions in GEMS could not form as reduction products and that other formation process such as condensation or irradiation are more likely.
A conceptual model linking functional gene expression and reductive dechlorination rates of chlorinated ethenes in clay rich groundwater sediment
DEFF Research Database (Denmark)
Bælum, Jacob; Chambon, Julie Claire Claudia; Scheutz, Charlotte
We used current knowledge of cellular processes involved in reductive dechlorination to develop a conceptual model to describe