Sample records for amorphous fe oxyhydroxides
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Lovley, D.R.; Phillips, E.J.P.
1986-10-01
The distribution of Fe(III), its availability for microbial reduction, and factors controlling Fe(III) availability were investigated in sediments from a freshwater site in the Potomac River Estuary. Fe(III) reduction in sediments incubated under anaerobic conditions and depth profiles of oxalate-extractable Fe(III) indicated that Fe(III) reduction was limited to depths of 4 cm or less, with the most intense Fe(III) reduction in the top 1 cm. In incubations of the upper 4 cm of the sediments, Fe(III) reduction was as important as methane production as a pathway for anaerobic electron flow because of the high rates of Fe(III) reduction in themore » 0- 0.5-cm interval. Most of the oxalate-extractable Fe(III) in the sediments was not reduced and persisted to a depth of at least 20 cm. The incomplete reduction was not the result of a lack of suitable electron donors. The oxalate-extractable Fe(III) that was preserved in the sediments was considered to be in a form other than amorphous Fe(III) oxyhydroxide, since synthetic amorphous Fe(III) oxyhydroxide, amorphous Fe(III) oxyhydroxide adsorbed onto clay, and amorphous Fe(III) oxyhydroxide saturated with adsorbed phosphate or fulvic acids were all readily reduced. Fe/sub 3/O/sub 4/ and the mixed Fe(III)-Fe(II) compound(s) that were produced during the reduction of amorphous Fe(III) oxyhydroxide in an enrichment culture were oxalate extractable but were not reduced, suggesting that mixed Fe(III)-Fe(II) compounds might account for the persistence of oxalate-extractable Fe(III) in the sediments.« less
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Lovley, D R; Phillips, E J
1986-10-01
The distribution of Fe(III), its availability for microbial reduction, and factors controlling Fe(III) availability were investigated in sediments from a freshwater site in the Potomac River Estuary. Fe(III) reduction in sediments incubated under anaerobic conditions and depth profiles of oxalate-extractable Fe(III) indicated that Fe(III) reduction was limited to depths of 4 cm or less, with the most intense Fe(III) reduction in the top 1 cm. In incubations of the upper 4 cm of the sediments, Fe(III) reduction was as important as methane production as a pathway for anaerobic electron flow because of the high rates of Fe(III) reduction in the 0- to 0.5-cm interval. Most of the oxalate-extractable Fe(III) in the sediments was not reduced and persisted to a depth of at least 20 cm. The incomplete reduction was not the result of a lack of suitable electron donors. The oxalate-extractable Fe(III) that was preserved in the sediments was considered to be in a form other than amorphous Fe(III) oxyhydroxide, since synthetic amorphous Fe(III) oxyhydroxide, amorphous Fe(III) oxyhydroxide adsorbed onto clay, and amorphous Fe(III) oxyhydroxide saturated with adsorbed phosphate or fulvic acids were all readily reduced. Fe(3)O(4) and the mixed Fe(III)-Fe(II) compound(s) that were produced during the reduction of amorphous Fe(III) oxyhydroxide in an enrichment culture were oxalate extractable but were not reduced, suggesting that mixed Fe(III)-Fe(II) compounds might account for the persistence of oxalate-extractable Fe(III) in the sediments. The availability of microbially reducible Fe(III) in surficial sediments demonstrates that microbial Fe(III) reduction can be important to organic matter decomposition and iron geochemistry. However, the overall extent of microbial Fe(III) reduction is governed by the inability of microorganisms to reduce most of the Fe(III) in the sediment.
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Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.
2008-01-01
Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).
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Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.
Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D
2015-12-15
U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.
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NASA Astrophysics Data System (ADS)
Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.
2010-12-01
Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.
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Samide, Adriana; Tutunaru, Bogdan
2011-01-01
A Schiff base, namely N-(2-hydroxybenzylidene) thiosemicarbazide (HBTC), was investigated as inhibitor for carbon steel in saline water (SW) using electrochemical measurements such as: potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The morphology of the surfaces before and after corrosion was examined by Scanning Electron Microscopy with Energy Dispersive X-ray Spectroscopy (SEM/EDS). The results showed that HBTC acts as corrosion inhibitor in SW by suppressing simultaneously the cathodic and anodic processes via adsorption on the surface which followed the Langmuir adsorption isotherm; the polarization resistance (R(p)) and inhibition efficiency (IE) increased with each HBTC concentration increase. SEM/EDS analysis showed at this stage that the main product of corrosion is a non-stoichiometric amorphous Fe(3+) oxyhydroxide, consisting of a mixture of Fe(3+) oxyhydroxides, α-FeOOH and/or γ-FeOOH, α-FeOOH/γ-FeOOH and Fe(OH)(3).
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NASA Astrophysics Data System (ADS)
Gunnars, Anneli; Blomqvist, Sven; Johansson, Peter; Andersson, Christian
2002-03-01
The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.
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Chemical Data for Precipitate Samples
Foster, Andrea L.; Koski, Randolph A.
2008-01-01
During studies of sulfide oxidation in coastal areas of Prince William Sound in 2005, precipitate samples were collected from onshore and intertidal locations near the Ellamar, Threeman, and Beatson mine sites (chapter A, fig. 1; table 7). The precipitates include jarosite and amorphous Fe oxyhydroxide from Ellamar, amorphous Fe oxyhydroxide from Threeman, and amorphous Fe oxyhydroxide, ferrihydrite, and schwertmannite from Beatson. Precipitates occurring in the form of loose, flocculant coatings were harvested using a syringe and concentrated in the field by repetitive decanting. Thicker accumulations were either scraped gently from rocks using a stainless steel spatula or were scooped directly into receptacles (polyethylene jars or plastic heavy-duty zippered bags). Most precipitate samples contain small amounts of sedimentary detritus. With three jarosite-bearing samples from Ellamar, an attempt was made to separate the precipitate from the heavy-mineral fraction of the sediment. In this procedure, the sample was stirred in a graduated cylinder containing deionized water. The jarosite-rich suspension was decanted onto analytical filter paper and air dried before analysis. Eleven precipitate samples from the three mine sites were analyzed in laboratories of the U.S. Geological Survey (USGS) in Denver, Colorado (table 8). Major and trace elements were determined by inductively coupled plasma-mass spectrometry following multiacid (HCl-HNO3-HClO4-HF) digestion (Briggs and Meier, 2002), except for mercury, which was analyzed by cold-vapor atomic absorption spectroscopy (Brown and others, 2002a). X-ray diffraction (XRD) analyses were performed on powdered samples (<200 mesh) by S. Sutley of the USGS. Additional details regarding sample preparation and detection limits are found in Taggert (2002). Discussions of the precipitate chemistry and associated microbial communities are presented in Koski and others (2008) and Foster and others (2008), respectively.
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Bacterial Formation of As(V) and As(III) Ferric Oxyhydroxides in Acid Mine Drainage.
NASA Astrophysics Data System (ADS)
Morin, G.; Juillot, F.; Lebrun, S.; Casiot, C.; Elbaz-Poulichet, F.; Bruneel, O.; Personne, J.; Leblanc, M.; Ildefonse, P.; Calas, G.
2002-12-01
The oxidation of dissolved Fe(II) which is often promoted by acidophilic bacteria in acid mine drainage (AMD) and some hot springs, leads to the precipitation of Fe(III) oxy-hydroxides which incorporate toxic elements within their structure or adsorb them at their surface, thus limiting their mobility. In such complex natural systems, synchrotron-based techniques as X-ray absorption spectroscopy offer the opportunity to monitor surface/solution interactions as well as redox changes affecting the mobility and toxicity of trace elements as arsenic. Spatial and seasonal variations of the (bio-) oxidation of Fe(II) and As(III), and the subsequent precipitation of As-Fe gels, were followed by XANES, XRD, and SEM along the CarnoulŠs AMD (Gard, France). Chemical and mineralogical data collected on sediments, stromatolite, and bioassay samples showed that some indigenous bacteria living in the As-rich CarnoulŠs water ([As] = up to 350 mg.l-1) play an important role in the nature and composition of the solid phases that sequester arsenic at the site. The formation of nano-crystalline and amorphous As(III) ferric oxy-hydroxides has been related to the presence of bacteria able to oxidize Fe(II) but not As(III), which are only present in winter in the upstream area. A rare ferric arsenite sulfate oxy-hydroxide mineral was discovered in this context. Other types of bacteria, occurring in the downstream area whatever the season, are able to catalyze As(III) to As(V) oxidation and, provided that enough Fe(II) oxidizes, promote the formation of amorphous As(V) rich ferric oxy-hydroxides. These bacterially mediated reactions significantly reduce the concentration of dissolved As(III), which is more toxic and mobile than As(V), and might thus be helpful for designing As-removal processes. This work was supported by the French PEVS and ACI Ecologie Quantitative Programs and the PIRAMID EC program. ?Deceased, 26 October 1999 Juillot F., Ildefonse Ph., Morin G., Calas G., De Kersabiec A.M. and Benedetti M. Applied Geochemistry 8, 1031-1048 (1999). Morin G., Lecocq D., Juillot F., Ildefonse Ph., Calas Bull. Soc. Géol. Fr. 173, 281-291 (2002). Morin G., Juillot F., Casiot C., Bruneel O., Personné J-C., Elbaz-Poulichet F., Leblanc M., Ildefonse P. and Calas G. Environ. Sci. Technol (in review.)
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Lee, Eunjik; Park, Ah-Hyeon; Park, Hyun-Uk; Kwon, Young-Uk
2018-01-01
In this work, we present facile synthesis of amorphous Ni/Fe mixed (oxy)hydroxide (NiFe(H)) nanoparticles (NPs) and their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline media. a-NiFe(H) NPs have received lots of attention as OER electrocatalysts with many desirable properties. By using a simple sonochemical route, we prepared amorphous Ni and Fe-alkoxide (NiFe(A)) NPs whose composition can be controlled in the entire composition range (Ni 100-x Fe x , 0≤x≤1). These samples are composed of extremely small NiFe(A) NPs with Ni and Fe atoms homogeneously distributed. NiFe(A) NPs are readily converted into corresponding electrocatalytically active NiFe(H) NP by a simple electrochemical treatment. Electrochemical analysis data show that the OER activity of amorphous NiFe(H) samples follows the volcano-type trend when plotted against the Fe content. Ni 70 Fe 30 (H) sample showed the lowest overpotential of 292mV at 10mAcm -2 geo and the lowest Tafel slope of 30.4mVdec -1 , outperforming IrO x /C (326mV, 41.7mVdec -1 ). Our samples are highly durable based on the chronopotentiometry data at the current density of 10mAcm -2 geo for 2h which show that Ni 70 Fe 30 sample maintains the steady-state potential, contrary to the time-varying IrO x /C. Copyright © 2017 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan
2017-08-01
Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O2 on ferrihydrite surfaces should include an electrochemical pathway, i.e., electron transfer (ET) in the Mn(II)-Conduction Band (CB)Ferrihydrite-O2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e., ET in the Mn(II)-Fe(II, III)-O2 complexes and direct ET in the Mn(II)-O2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments.
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Sharif, M.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.
2008-01-01
Twenty one of 118 irrigation water wells in the shallow (25-30??m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (< 0.5 to 77????g/L) exceeding 10????g/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO3-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25??M hydroxylamine hydrochloride in 0.25??M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO3 extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70????g/kg) exchangeable As is only present at shallow depth (0-1??m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r = 0.83) and hot HNO3 (r = 0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO3. Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO3) is positively correlated (r = 0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO42- reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area. ?? 2008 Elsevier B.V. All rights reserved.
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Geochemistry of molybdenum in some stream sediments and waters
NASA Astrophysics Data System (ADS)
Kaback, Dawn S.; Runnells, Donald D.
1980-03-01
Elevated concentrations of Mo are present in both the waters and sediments of Tenmile Creek, downstream from the large Mo deposit at Climax. Colorado. Concentrations of Mo reach a maximum of 10mg/1 in the water and 384μ/g in the (-) 80 mesh fraction of the sediment. The Mo anomaly extends for more than 80 km downstream from Climax, and results from the mining and milling at Climax. Background Mo concentrations in the nearby mountainous area are < 10μg/l (water) and < 5μg/g (sediment). Immediately below three small unmined Mo-rich orebodies elsewhere in Colorado < 3μg/l Mo are present in the waters and 20-30μg/g Mo in the fine fraction of the sediments. The Mo in the sediment of Tenmile Creek is chiefly adsorbed on coatings of amorphous Fe oxyhydroxide. and is similar to its form below two small, unmined Mo deposits. Mining has not changed the character of the chemical processes responsible for Mo dispersion from the Climax site. A modified version of the WATEQF computer program ( PLUMMERet al., 1976) predicts that Tenmile Creek is undersaturated with respect to ferrimolybdite. molybdenite, powellite, and ilsemannite. The Mo in the stream water occurs as the molybdate ion which can be adsorbed on amorphous Fe oxyhydroxides. These predictions are supported by the absence of Mo minerals in the sediment of Tenmile Creek.
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Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F
2013-01-01
Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L2,3 absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)–Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension. PMID:23038172
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Luef, Birgit; Fakra, Sirine C.; Csencsits, Roseann
2013-02-04
Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III) bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Further, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on sitemore » and subsequently examined using correlated 2- and 3- dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). Most cells had their outer membranes decorated with up to 150 nm diameter aggregates composed of a few nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well studied group of FeRB. STXM results at the Fe L2,3 absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell-surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.« less
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Luef, Birgit; Fakra, Sirine C; Csencsits, Roseann; Wrighton, Kelly C; Williams, Kenneth H; Wilkins, Michael J; Downing, Kenneth H; Long, Philip E; Comolli, Luis R; Banfield, Jillian F
2013-02-01
Iron-reducing bacteria (FeRB) play key roles in anaerobic metal and carbon cycling and carry out biogeochemical transformations that can be harnessed for environmental bioremediation. A subset of FeRB require direct contact with Fe(III)-bearing minerals for dissimilatory growth, yet these bacteria must move between mineral particles. Furthermore, they proliferate in planktonic consortia during biostimulation experiments. Thus, a key question is how such organisms can sustain growth under these conditions. Here we characterized planktonic microbial communities sampled from an aquifer in Rifle, Colorado, USA, close to the peak of iron reduction following in situ acetate amendment. Samples were cryo-plunged on site and subsequently examined using correlated two- and three-dimensional cryogenic transmission electron microscopy (cryo-TEM) and scanning transmission X-ray microscopy (STXM). The outer membranes of most cells were decorated with aggregates up to 150 nm in diameter composed of ∼3 nm wide amorphous, Fe-rich nanoparticles. Fluorescent in situ hybridization of lineage-specific probes applied to rRNA of cells subsequently imaged via cryo-TEM identified Geobacter spp., a well-studied group of FeRB. STXM results at the Fe L(2,3) absorption edges indicate that nanoparticle aggregates contain a variable mixture of Fe(II)-Fe(III), and are generally enriched in Fe(III). Geobacter bemidjiensis cultivated anaerobically in the laboratory on acetate and hydrous ferric oxyhydroxides also accumulated mixed-valence nanoparticle aggregates. In field-collected samples, FeRB with a wide variety of morphologies were associated with nano-aggregates, indicating that cell surface Fe(III) accumulation may be a general mechanism by which FeRB can grow while in planktonic suspension.
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Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide
Balistrieri, L.S.; Chao, T.T.
1990-01-01
This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.
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Origin of middle rare earth element enrichments in acid waters of a Canadian high Arctic lake.
NASA Astrophysics Data System (ADS)
Johannesson, Kevin H.; Zhou, Xiaoping
1999-01-01
-Middle rare earth element (MREE) enriched rock-normalized rare earth element (REE) patterns of a dilute acidic lake (Colour Lake) in the Canadian High Arctic, were investigated by quantifying whole-rock REE concentrations of rock samples collected from the catchment basin, as well as determining the acid leachable REE fraction of these rocks. An aliquot of each rock sample was leached with 1 N HNO 3 to examine the readily leachable REE fraction of each rock, and an additional aliquot was leached with a 0.04 M NH 2OH · HCl in 25% (v/v) CH 3COOH solution, designed specifically to reduce Fe-Mn oxides/oxyhydroxides. Rare earth elements associated with the leachates that reacted with clastic sedimentary rock samples containing petrographically identifiable Fe-Mn oxide/oxyhydroxide cements and/or minerals/amorphous phases, exhibited whole-rock-normalized REE patterns similar to the lake waters, whereas whole-rock-normalized leachates from mafic igneous rocks and other clastic sedimentary rocks from the catchment basin differed substantially from the lake waters. The whole-rock, leachates, and lake water REE data support acid leaching or dissolution of MREE enriched Fe-Mn oxides/oxyhydroxides contained and identified within some of the catchment basin sedimentary rocks as the likely source of the unique lake water REE patterns. Solution complexation modelling of the REEs in the inflow streams and lake waters indicate that free metal ions (e.g., Ln 3+, where Ln = any REE) and sulfate complexes (LnSO 4+) are the dominant forms of dissolved REEs. Consequently, solution complexation reactions involving the REEs during weathering, transport to the lake, or within the lake, cannot be invoked to explain the MREE enrichments observed in the lake waters.
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Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean
Chan, L.-H.; Hein, J.R.
2007-01-01
To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO2. The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.
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NASA Technical Reports Server (NTRS)
Banin, A.
1988-01-01
A mineralogical model for the Mars fine soil that includes as major components smectite clays absorbed and coated with amorphous iron oxyhydroxides and perhaps mixed with small amounts of better-crystalized iron oxides as separate phases is proposed. Also present as accessory minerals are sulfate minerals such as kieserite (MgSO4.H2O) and/or anhydrite (CaSO4), rutile (TiO2), and maghemite (Fe2O3) or magnetite (Fe3O4), the last two as magnetic components. Carbonates may be present at low concentrations only (less than 1 to 2 pct). However, a prime question to be addressed by a Mars Sample Return Mission shall be related to the mineralogical composition of the soil, and its spatial variability.
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Influence of humic acid concentration on nTiO2 attachment to quartz sand and Fe-coated quartz sand
NASA Astrophysics Data System (ADS)
Cheng, T.; Wu, Y.
2016-12-01
The transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by nTiO2 attachment to sediment grains. The objective of this study is to investigate the role of humic acid (HA) in the attachment of nTiO2 to sand at low HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in groundwater can be elucidated. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the transport of negatively-charged colloids, may influence nTiO2 in different manners. Attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at fixed pH. Experimental results show that at pH 5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in relatively high nTiO2 attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in low nTiO2 attachment. At pH 9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the attachment of nTiO2. This study demonstrates that the changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption could be a key factor that controls the attachment of nTiO2 to sediment grains.
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NASA Astrophysics Data System (ADS)
Peng, Xiaotong; Chen, Shun; Xu, Hengchao
2013-12-01
small hot spring that is informally called "Fe-waterfall spring" and is located in the Rehai geothermal area discharges hot (42 to 73°C), near-neutral (pH = 7.65) Fe-rich water. Submerged reddish precipitates are composed largely of ferrihydrite, goethite, lepidocrocite, opal-A, quartz, and anorthite, as revealed by X-ray diffraction (XRD) and Mössbauer spectroscopy. Molecular phylogenetic analysis demonstrates that the bacterial community in these precipitates is mainly composed of Cyanobacteria, Planctomycetes, β-proteobacteria, Deinococci-Thermus, and Chlorobi. Scanning electron microscopy and high-resolution transmission electron microscopy examinations show that abundant sheath-like Fe oxyhydroxides, which exhibit different morphologies and sizes, are present in Fe-rich precipitates. These sheath-like structures are composed of ferrihydrite rather than more crystalline lepidocrocite or goethite. Energy-dispersive X-ray spectrometer, scanning transmission electron microscopy, and nano secondary ion mass spectrometry reveal that they are mainly composed of Fe, Si, and O, together with some trace elements. Most of the sheath-like structures are not morphologically comparable to biogenic Fe oxyhydroxides produced by known chemolithotrophic Fe oxidizers, which is consistent with the fact that no chemolithotrophic Fe oxidizers were identified by molecular analysis in the precipitates. We suggest that the sheath-like Fe oxyhydroxides are formed through passive Fe sorption and nucleation onto the cell walls of various thermophiles rather than by the direct metabolic activities of chemolithotrophic Fe oxidizers. Biogenic sheath-like Fe oxyhydroxides in Fe-waterfall spring have important implications for geochemical cycles driven by microorganisms, the origin of microfossils, and the formation of banded iron formations (BIFs) in the Archean ocean.
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Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge
DOE Office of Scientific and Technical Information (OSTI.GOV)
Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.
2008-05-22
Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (mu XRF), X-ray absorption spectroscopy (mu EXAFS), and X-ray diffraction (mu XRD) in conjunction with focusedmore » ion beam (FIB) sectioning, and highresolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe1-xS, 0<_ x<_ 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe mu EXAFS spectroscopy and mu XRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O6 octahedral linkages. Double corner-sharing Fe-O6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that microbiologically produced Fe-complexing ligands may play critical roles in both the delivery of Fe(II) to oxidases, and the limited Fe(III) oxyhydroxide crystallinity observed within the biofilm. Our research provides insight into the structure and formation of naturally occurring, microbiologically produced Fe oxyhydroxide minerals in the deep-sea. We describe the initiation of microbial seafloor weathering, and the morphological and mineralogical signals that result from that process. Our observations provide a starting point from which progressively older and more extensively weathered seafloor sulfide minerals may be examined, with the ultimate goal of improved interpretation of ancient microbial processes and associated biological signatures.« less
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Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge
NASA Astrophysics Data System (ADS)
Toner, Brandy M.; Santelli, Cara M.; Marcus, Matthew A.; Wirth, Richard; Chan, Clara S.; McCollom, Thomas; Bach, Wolfgang; Edwards, Katrina J.
2009-01-01
Here we examine Fe speciation within Fe-encrusted biofilms formed during 2-month seafloor incubations of sulfide mineral assemblages at the Main Endeavor Segment of the Juan de Fuca Ridge. The biofilms were distributed heterogeneously across the surface of the incubated sulfide and composed primarily of particles with a twisted stalk morphology resembling those produced by some aerobic Fe-oxidizing microorganisms. Our objectives were to determine the form of biofilm-associated Fe, and identify the sulfide minerals associated with microbial growth. We used micro-focused synchrotron-radiation X-ray fluorescence mapping (μXRF), X-ray absorption spectroscopy (μΕXAFS), and X-ray diffraction (μXRD) in conjunction with focused ion beam (FIB) sectioning, and high resolution transmission electron microscopy (HRTEM). The chemical and mineralogical composition of an Fe-encrusted biofilm was queried at different spatial scales, and the spatial relationship between primary sulfide and secondary oxyhydroxide minerals was resolved. The Fe-encrusted biofilms formed preferentially at pyrrhotite-rich (Fe 1-xS, 0 ⩽ x ⩽ 0.2) regions of the incubated chimney sulfide. At the nanometer spatial scale, particles within the biofilm exhibiting lattice fringing and diffraction patterns consistent with 2-line ferrihydrite were identified infrequently. At the micron spatial scale, Fe μEXAFS spectroscopy and μXRD measurements indicate that the dominant form of biofilm Fe is a short-range ordered Fe oxyhydroxide characterized by pervasive edge-sharing Fe-O 6 octahedral linkages. Double corner-sharing Fe-O 6 linkages, which are common to Fe oxyhydroxide mineral structures of 2-line ferrihydrite, 6-line ferrihydrite, and goethite, were not detected in the biogenic iron oxyhydroxide (BIO). The suspended development of the BIO mineral structure is consistent with Fe(III) hydrolysis and polymerization in the presence of high concentrations of Fe-complexing ligands. We hypothesize that microbiologically produced Fe-complexing ligands may play critical roles in both the delivery of Fe(II) to oxidases, and the limited Fe(III) oxyhydroxide crystallinity observed within the biofilm. Our research provides insight into the structure and formation of naturally occurring, microbiologically produced Fe oxyhydroxide minerals in the deep-sea. We describe the initiation of microbial seafloor weathering, and the morphological and mineralogical signals that result from that process. Our observations provide a starting point from which progressively older and more extensively weathered seafloor sulfide minerals may be examined, with the ultimate goal of improved interpretation of ancient microbial processes and associated biological signatures.
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NASA Technical Reports Server (NTRS)
Parkin, K. M.; Burns, R. G.
1980-01-01
It is pointed out that transition metal ions in silicate minerals, glasses, and crystalline and amorphous oxyhydroxides and salts contribute to the visible-near infrared spectral profiles of planetary surfaces. Investigations are conducted to obtain spectral information which might be helpful in the interpretation of the remote-sensed spectra of planetary surfaces. A description is presented of the results of high temperature crystal field spectral measurements of a variety of heated minerals containing Cr(3+), Fe(3+), Fe(++), and Mn(++) ions in different coordination symmetries, taking into account a correlation of the temperature-induced variations with those previously observed for octahedrally coordinated Fe(++)-bearing silicates. The employed experimental methods are also discussed, giving attention to the preparation of the samples, the determination of the absorption spectra, electron microprobe analyses, and the curve fitting procedure.
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Stability of nTiO2 particles and their attachment to sand: Effects of humic acid at different pH.
Wu, Yang; Cheng, Tao
2016-01-15
The fate and transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by the stability of nTiO2 and their attachment to sediment grains. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively-charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand at HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in natural systems can be elucidated. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at pH5 and 9. Results show that at pH5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in nTiO2 aggregation and attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in stable nTiO2 suspension and low nTiO2 attachment. At pH9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the stability and attachment of nTiO2. Overall, this study shows that changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption is a key factor that influences the stability and attachment of nTiO2. Copyright © 2015 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Fisher-Power, L.; Cheng, T.
2017-12-01
Transport of engineered nanoparticles (ENP) in subsurface environments has important implications to water quality and soil contamination. Although extensive research has been conducted to understand the effects of water chemistry on ENP transport, less attention has been paid to influences from the transport medium/matrix. The objective of this research is to investigate the effects of natural organic matter (NOM) and Fe/Al oxyhydroxides in a natural sediment on ENP transport. A sediment was collected and separated into four portions, one of which was unmodified, and the others treated to remove specific components (organic matter, Fe/Al oxyhydroxides, or both organic matter and Fe/Al oxyhydroxides). Transport of nanoscale titanium dioxide (nTiO2) in columns packed with quartz sand and each of the four types of the sediment under water-saturated conditions was studied. Our results showed that nTiO2 transport was strongly influenced by pH and sediment composition. When influent pH = 5, nTiO2 transport in all the sediments was low, as positively-charged nTiO2 was attracted to negatively charged NOM, quartz, and other minerals. nTiO2 transport was slightly enhanced in columns packed with untreated sediment or Fe/Al oxyhydroxides removed sediment due to dissolved organic matter generated by the partial dissolution of NOM, which adsorbed onto nTiO2 surface and reversed its zeta potential to negative. When influent pH = 9, nTiO2 transport was generally high since negatively-charged nTiO2 was repelled by negatively charged transport medium. However, in columns packed with the organic matter removed sediment or the Fe/Al oxyhydroxides removed sediment, nTiO2 transport was low. This was attributable to pH buffering by the sediment, which decreased pore water pH in the column, resulting in zeta potential change and electrostatic attraction between Fe/Al oxyhydroxides and nTiO2. This research demonstrates that electrostatic forces between nTiO2 and mineral/organic components in natural sediments is a key factor that controls nTiO2 retention and transport, and that both NOM and Fe/Al oxyhydroxides may substantially influence nTiO2 transport.
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The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars
NASA Technical Reports Server (NTRS)
Morris, Richard V.; Ming,, Douglas W.; Blake, David; Vaniman, David; Bish, David L; Chipera, Steve; Downs, Robert; Morrison, Shaunna; Gellert, Ralf; Campbell, Iain;
2013-01-01
Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.
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Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines
NASA Astrophysics Data System (ADS)
Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee
2017-01-01
The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic brine lakes and acid mine drainage locations that contain precipitated iron oxyhydroxides.
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NASA Astrophysics Data System (ADS)
Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping
2017-03-01
Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co0.54Fe0.46OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co0.54Fe0.46OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application.
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Zhang, Xinyu; An, Li; Yin, Jie; Xi, Pinxian; Zheng, Zhiping; Du, Yaping
2017-03-08
Rational design of high efficient and low cost electrocatalysts for oxygen evolution reaction (OER) plays an important role in water splitting. Herein, a general gelatin-assisted wet chemistry method is employed to fabricate well-defined iron oxy-hydroxides and transitional metal doped iron oxy-hydroxides nanomaterials, which show good catalytic performances for OER. Specifically, the Co-doped iron oxy-hydroxides (Co 0.54 Fe 0.46 OOH) show the excellent electrocatalytic performance for OER with an onset potential of 1.52 V, tafel slope of 47 mV/dec and outstanding stability. The ultrahigh oxygen evolution activity and strong durability, with superior performance in comparison to the pure iron oxy-hydroxide (FeOOH) catalysts, originate from the branch structure of Co 0.54 Fe 0.46 OOH on its surface so as to provide many active edge sites, enhanced mass/charge transport capability, easy release oxygen gas bubbles, and strong structural stability, which are advantageous for OER. Meanwhile, Co-doping in FeOOH nanostructures constitutes a desirable four-electron pathway for reversible oxygen evolution and reduction, which is potentially useful for rechargeable metal-air batteries, regenerative fuel cells, and other important clean energy devices. This work may provide a new insight into constructing the promising water oxidation catalysts for practical clean energy application.
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Dekov, V.M.; Kamenov, George D.; Savelli, C.; Stummeyer, Jens; Thiry, M.; Shanks, Wayne C.; Willingham, A.L.; Boycheva, T.B.; Rochette, P.; Kuzmann, E.; Fortin, D.; Vertes, A.
2009-01-01
A sediment core taken from the south-east slope of the Eolo Seamount is composed of alternating red-brown and light-brown to bluish-grey layers with signs of re-deposition in the middle-upper section. The red-brown layers are Fe-rich metalliferous sediments formed as a result of low-temperature (??? 77????C) hydrothermal discharge, whereas the bluish-grey layers most probably originated from background sedimentation of Al-rich detrital material. The metalliferous layers are composed mainly of Si-rich goethite containing some Al. Co-precipitation of hydrothermally released SiO44- and Fe2+ as amorphous or poorly crystalline Fe-Si-oxyhydroxides explains the high Si concentration in goethite. The elevated Al content of the goethite is fairly unusual, but reflects the extremely high background Al content of the Tyrrhenian seawater due to the high eolian terrigenous flux from the Sahara desert. The Sr and Nd isotope data suggest that the Eolo metalliferous sediments are the product of a 3-component mixture: hydrothermal fluid, seawater, and detrital material (Saharan dust and Aeolian Arc material). The enrichment in Fe, P, As, Mo, Cd, Be, Sb, W, Y, V, depletion in REE and transition elements (Cu, Co, Ni, Zn) and the REE distribution patterns support the low-temperature hydrothermal deposition of the metalliferous layers. The hydrothermal field is located in a seawater layer of relative O2 depletion, which led to a significant fractionation of the hydrothermally emitted Fe and Mn. Fe-oxyhydroxides precipitated immediately around the vents whereas Mn stayed in solution longer and the Mn-oxides precipitated higher up on the seamount slope in seawater with relatively higher O2 levels. High seismic activity led to sediment re-deposition and slumping of the Mn-rich layers down slope and mixing with the Fe-rich layers. ?? 2009 Elsevier B.V. All rights reserved.
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Baken, Stijn; Verbeeck, Mieke; Verheyen, Dries; Diels, Jan; Smolders, Erik
2015-03-15
Redox reactions involving iron (Fe) strongly affect the mobility of phosphorus (P) and its migration from agricultural land to freshwater. We studied the transfer of P from groundwater to open drainage ditches in an area where, due to Fe(II) rich groundwater, the sediments of these ditches contain accumulated Fe oxyhydroxides. The average P concentrations in the groundwater feeding two out of three studied drainage ditches exceeded environmental limits for freshwaters by factors 11 and 16, but after passing through the Fe-rich sediments, the P concentrations in the ditch water were below these limits. In order to identify the processes which govern Fe and P mobility in these systems, we used diffusive equilibration in thin films (DET) to measure the vertical concentration profiles of P and Fe in the sediment pore water and in the ditchwater. The Fe concentrations in the sediment pore water ranged between 10 and 200 mg L(-1) and exceeded those in the inflowing groundwater by approximately one order of magnitude, due to reductive dissolution of Fe oxyhydroxides in the sediment. The dissolved P concentrations only marginally increased between groundwater and sediment pore water. In the poorly mixed ditchwater, the dissolved Fe concentrations decreased towards the water surface due to oxidative precipitation of fresh Fe oxyhydroxides, and the P concentrations decreased more sharply than those of Fe. These observations support the view that the dynamics of Fe and P are governed by reduction reactions in the sediment and by oxidation reactions in the ditchwater. In the sediment, reductive dissolution of P-containing Fe oxyhydroxides causes more efficient solubilization of Fe than of P, likely because P is buffered by adsorption on residual Fe oxyhydroxides. Conversely, in the ditchwater, oxidative precipitation causes more efficient immobilization of P than of Fe, due to ferric phosphate formation. The combination of these processes yields a natural and highly efficient sink for P. It is concluded that, in Fe-rich systems, the fate of P at the sediment-water interface is determined by reduction and oxidation of Fe. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Paktunc, D.; Foster, A.; Heald, S.; Laflamme, G.
2004-01-01
The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO4??2H2O), ferric arsenates, arseniosiderite (Ca2Fe3 (AsO4)3O2??3H2O), Ca-Fe arsenates, pharmacosiderite (KFe4 (AsO4)3(OH)4??6-7H2O), jarosite (K2Fe6(SO4)4 (OH)12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 A?? and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore. ?? 2004 Elsevier Ltd.
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NASA Astrophysics Data System (ADS)
Paktunc, Dogan; Foster, Andrea; Heald, Steve; Laflamme, Gilles
2004-03-01
The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO 4·2H 2O), ferric arsenates, arseniosiderite (Ca 2Fe 3(AsO 4) 3O 2·3H 2O), Ca-Fe arsenates, pharmacosiderite (KFe 4(AsO 4) 3(OH) 4·6-7H 2O), jarosite (K 2Fe 6(SO 4) 4(OH) 12) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%. Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As 5+in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides. The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.
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Arsenic associations in sediments from shallow aquifers of northwestern Hetao Basin, Inner Mongolia
Deng, Y.; Wang, Y.; Ma, T.; Yang, H.; He, J.
2011-01-01
Understanding the mechanism of arsenic mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Hetao Basin in Inner Mongolia, northern China. Aquifer geochemistry was characterized at three field sites (SH, HF, TYS) in Hangjinhouqi County of northwestern Hetao Basin. The results of bulk geochemistry analysis of sediment samples indicated that total As concentrations have a range of 6. 8-58. 5 mg/kg, with a median of 14. 4 mg/kg. The highest As concentrations were found at 15-25 m depth. In the meanwhile, the range of As concentration in the sediments from background borehole is 3-21. 8 mg/kg, with a median value of 9 mg/kg. The As sediments concentrations with depth from the SH borehole were correlated with the contents of Fe, Sb, B, V, total C and total S. Generally, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments. Distinct lithology profile and different geochemical characteristics of aquifer sediments indicate the sediments are associated with different sources and diverse sedimentary environments. Up to one third of arsenic in the sediments could be extracted by ammonium oxalate, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. Sequential extraction results indicate that arsenic occurs as strongly adsorbed on and/or co-precipitated with amorphous Fe oxyhydroxides in sediments accounting for 35 and 20%, respectively, of the total contents of arsenic. The release of As into groundwater may occur by desorption from the mineral surface driven by reductive dissolution of the Fe oxide minerals. Furthermore, small proportions of As associated with iron sulfides occur in the reductive sediments. ?? 2011 Springer-Verlag.
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Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.
2008-01-01
The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.
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Liu, Airong; Zhang, Wei-xian
2014-09-21
An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.
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Grenne, Tor; Slack, John F.
2003-01-01
The jaspers are interpreted to record colloidal fallout from one or more hydrothermal plumes, followed by maturation (ageing) of an Si-Fe-oxyhydroxide gel, on and beneath the Ordovician sea floor. Small hematitic filaments in the jaspers reflect bacteria-catalysed oxidation of Fe2+ within the plume. The larger tubular filaments resulted from either microbial activity or inorganic self-organized mineral growth of Fe-oxyhydroxide within the Si-Fe-oxyhydroxide gel after deposition on the sea floor, prior to more advanced maturation of the gel as represented by the spheroidal and botryoidal silica-hematite textures. Bleaching and hematite±epidote growth are interpreted to reflect heat and fluids generated during deposition of basaltic sheet flows on top of the gels.
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NASA Astrophysics Data System (ADS)
Tresintsi, Sofia; Simeonidis, Konstantinos; Mitrakas, Manassis
2013-04-01
Iron oxy-hydroxides are well defined As(V) adsorbents dominating in water treatment market. The main drawback of these adsorbents, as well as of all commercial one, is their significantly low adsorption capacity for As(III). A breakthrough for improving As(III) adsorption of iron oxy-hydroxides may come by the MnO2incorporation. However, MnO2 decreases the total arsenic capacity proportionally to its percentage since its efficiency for As(V) is much lower than that of an iron oxy-hydroxide. It is concluded that an ideal adsorbent capable for high and simultaneous As(III) and As(V) removal should be consisted of a binary Fe(III)-Mn(IV) oxy-hydroxide both efficient for As(III) oxidation, due to Mn(IV) presence, and capture of As(V) due to a high positively surface charge density. This work studies the optimum parameters at the synthesis of single Fe and binary Fe/Mn oxy-hydroxides in a continuous flow kilogram-scale production reactor through the precipitation of FeSO4 in the pH range 3-12, under intense oxidative conditions using H2O2/KMnO4, that maximize arsenic adsorption. The evaluation of their efficiency was based on its As(III) and As(V) adsorption capacity (Q10-index) at equilibrium concentration equal to drinking water regulation limit (Ce= 10 μg/L) in NSF challenge water. The pH of synthesis was found to decisively affect, the structure, surface configuration and Q10-index. As a result, both single Fe and binary Fe/Mn oxy-hydroxides prepared at pH 4, which consist of schwertmannite and Mn(IV)-feroxyhyte respectively, were qualified according to their highest Q10-index of 13±0.5 μg As(V)/ mg for a residual arsenic concentration of 10 μg/L at an equilibrium pH 7. The high surface charge and the activation of an ion-exchange mechanism between SO42- adsorbed in the Stern layer and arsenate ions were found to significantly contribute to the increased adsorption capacity. The Q10-index for As(III) of Fe/Mn adsorbent at equilibrium pH 7 was 6.7 μg/mg, which is 3.5 times greater of that for single Fe one (1.9 μg/mg), although it is significantly lower of the respective for As(V). However, Fe/Mn oxy-hydroxide present almost equal adsorption capacity for both arsenic species in the pH range 7.5-8. The As(III) adsorption capacity of Fe/Mn oxy-hydroxides is positively affected by the Mn content and the redox potential values at equilibrium pH 6-7. The corresponding Q10-index values observed in rapid scale column tests were in agreement with those of batch experiments, illustrating the improved efficiency of the qualified adsorbent compared to the common commercial arsenic adsorbents. Acknowledgement This work was supported by the European Commission FP7/Research for SMEs "AquAsZero", Project No: 232241.
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Paleozoic and Mesozoic silica-rich seawater: Evidence from hematitic chert (jasper) deposits
Grenne, Tor; Slack, J.F.
2003-01-01
Laterally extensive beds of highly siliceous, hematitic chert (jasper) are associated with many volcanogenic massive sulfide (VMS) deposits of Late Cambrian to Early Cretaceous age, yet are unknown in analogous younger (including modern) settings. Textural studies suggest that VMS-related jaspers in the Ordovician Løkken ophiolite of Norway were originally deposited as Si- and Fe-rich gels that precipitated from hydrothermal plumes as colloidal silica and iron-oxyhydroxide particles. Rare earth element patterns and Ge/Si ratios of the jaspers reflect precipitation from plumes having seawater dilution factors of 103 to 104, similar to modern examples. We propose that silica in the ancient jaspers is not derived from submarine hydrothermal fluids-as suggested by previous workers-but instead was deposited from silic-rich sea-water. Flocculation and precipitation of the silica were triggered inorganically by the bridging effect of positively charged iron oxyhydroxides in the hydrothermal plume. A model involving amorphous silica (opal-A) precursors to the jaspers suggests that silica contents of Cambrian-Early Cretaceous oceans were at least 110 mg/L SiO2, compared to values of 40-60 mg/L SiO2 estimated in other studies. The evolution of ancient silica-rich to modern Fe-rich precipitates in submarine-hydrothermal plumes reflects a changeover from silica-saturated to silica-depleted seawater through Phanerozoic time, due mainly to ocean-wide emergence of diatoms in the Cretaceous.
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Novel interpretation of the mean structure of feroxyhyte
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sestu, Matteo, E-mail: msestu@unica.it; Carta, Daniela; Casula, Maria F.
2015-05-15
The structure of the iron oxyhydroxide called feroxyhyte (δ-FeOOH), which shows an elusive X-ray powder diffraction pattern, has been represented so far using models describing a mean structure based on the crystalline network of the iron(III) oxide hematite (α-Fe{sub 2}O{sub 3}). In this paper, a novel description of the mean structure of feroxyhyte is presented, which is based on the structure of the thermodynamically stable iron oxyhydroxide goethite. Starting from different local arrangements present in the goethite network, a mean structural model is determined which shows an X-ray powder diffraction pattern almost coincident with previous studies. This outcome enables tomore » integrate the structure of feroxyhyte among those of other well characterized iron oxyhydroxides. - Graphical abstract: The structure of the iron oxy-hydroxide feroxyhyte can be described by local arrangements present in the goethite network. - Highlights: • The structure of feroxyhyte (δ-FeOOH) proposed in literature is discussed. • The structure of goethite (α-FeOOH) is analyzed. • A structural relationship between feroxyhyte and goethite is found. • New interpretation of the mean structure of δ-FeOOH is given.« less
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Kostka, Joel E.; Dalton, Dava D.; Skelton, Hayley; Dollhopf, Sherry; Stucki, Joseph W.
2002-01-01
Smectite clay minerals are abundant in soils and sediments worldwide and are typically rich in Fe. While recent investigations have shown that the structural Fe(III) bound in clay minerals is reduced by microorganisms, previous studies have not tested growth with clay minerals as the sole electron acceptor. Here we have demonstrated that a pure culture of Shewanella oneidensis strain MR-1 as well as enrichment cultures of Fe(III)-reducing bacteria from rice paddy soil and subsurface sediments are capable of conserving energy for growth with the structural Fe(III) bound in smectite clay as the sole electron acceptor. Pure cultures of S. oneidensis were used for more detailed growth rate and yield experiments on various solid- and soluble-phase electron acceptors [smectite, Fe(III) oxyhydroxide FeOOH, Fe(III) citrate, and oxygen] in the same minimal medium. Growth was assessed as direct cell counts or as an increase in cell carbon (measured as particulate organic carbon). Cell counts showed that similar growth of S. oneidensis (108 cells ml−1) occurred with smectitic Fe(III) and on other Fe forms [amorphous Fe(III) oxyhydroxide, and Fe citrate] or oxygen as the electron acceptor. In contrast, cell yields of S. oneidensis measured as the increase in cell carbon were similar on all Fe forms tested while yields on oxygen were five times higher, in agreement with thermodynamic predictions. Over a range of particle loadings (0.5 to 4 g liter−1), the increase in cell number was highly correlated to the amount of structural Fe in smectite reduced. From phylogenetic analysis of the complete 16S rRNA gene sequences, a predominance of clones retrieved from the clay mineral-reducing enrichment cultures were most closely related to the low-G+C gram-positive members of the Bacteria (Clostridium and Desulfitobacterium) and the δ-Proteobacteria (members of the Geobacteraceae). Results indicate that growth with smectitic Fe(III) is similar in magnitude to that with Fe(III) oxide minerals and is dependent upon the mineral surface area available. Iron(III) bound in clay minerals should be considered an important electron acceptor supporting the growth of bacteria in soils or sedimentary environments. PMID:12450850
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Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite
NASA Astrophysics Data System (ADS)
Jones, Adele M.; Collins, Richard N.; Waite, T. David
2017-12-01
The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II).
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NASA Astrophysics Data System (ADS)
Bligh, Mark W.; Waite, T. David
2010-10-01
While chemical reactions that take place at the surface of amorphous ferric oxides (AFO) are known to be important in aquatic systems, incorporation of these reactions into kinetic models is hindered by a lack of ability to reliably quantify the reactivity of the surface and the changes in reactivity that occur over time. Long term decreases in the reactivity of iron oxides may be considered to result from changes in the molecular structure of the solid, however, over shorter time scales where substantial aggregation may occur, the mechanisms of reactivity loss are less clear. Precipitation of AFO may be described as a combination of homogeneous and heterogeneous reactions, however, despite its potentially significant role, the latter reaction is usually neglected in kinetic models of aquatic processes. Here, we investigate the role of AFO in scavenging dissolved inorganic ferric (Fe(III)) species (Fe') via the heterogeneous precipitation reaction during the net dissociation of organically complexed Fe(III) in seawater. Using sulfosalicylic acid (SSA) as a model ligand, AFO was shown to play a significant role in inducing the net dissociation of the Fe-SSA complexes with equations describing both the heterogeneous precipitation reaction and the aging of AFO being required to adequately describe the experimental data. An aggregation based mechanism provided a good description of AFO aging over the short time scale of the experiments. The behaviour of AFO described here has implications for the bioavailability of iron in natural systems as a result of reactions involving AFO which are recognised to occur over time scales of minutes, including adsorption of Fe' and AFO dissolution, precipitation and ageing.
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Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek
2011-08-29
The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Precipitation pathways for ferrihydrite formation in acidic solutions
Zhu, Mengqiang; Khalid, Syed; Frandsen, Cathrine; ...
2015-10-03
In this study, iron oxides and oxyhydroxides form via Fe 3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe 3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe 3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H 2O) 6 3+, μ-oxo aquo dimers and ferrihydrite, and that with time, themore » μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.« less
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Biswas, Ashis; Hendry, M Jim; Essilfie-Dughan, Joseph
2017-02-01
This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO 4 2- in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91μg/L) and rock-drain effluent (median: 0.31μg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley. Copyright © 2016 Elsevier B.V. All rights reserved.
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Goldsmith, Zachary K; Harshan, Aparna K; Gerken, James B; Vörös, Márton; Galli, Giulia; Stahl, Shannon S; Hammes-Schiffer, Sharon
2017-03-21
NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni 2+ to Ni 3+ , followed by oxidation to a mixed Ni 3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fe-doped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe 4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixed-metal oxidation states in heterogeneous catalysts.
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Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.; Galli, Giulia; Stahl, Shannon S.
2017-01-01
NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fe-doped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixed-metal oxidation states in heterogeneous catalysts. PMID:28265083
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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
2015-09-01
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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.
2017-03-06
NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast,more » absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.« less
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Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters
Jubb, Aaron M.; Eskelsen, Jeremy R.; Yin, Xiangping Lisa; ...
2018-04-04
Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with amore » suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+Fe 2 3+O 4) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.« less
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Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jubb, Aaron M.; Eskelsen, Jeremy R.; Yin, Xiangping Lisa
Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with amore » suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+Fe 2 3+O 4) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.« less
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Sehn, Janaína L; de Leão, Felipe B; da Boit, Kátia; Oliveira, Marcos L S; Hidalgo, Gelsa E; Sampaio, Carlos H; Silva, Luis F O
2016-03-01
Detailed geochemistry similarities between the burning coal cleaning rejects (BCCRs) and non-anthropogenic geological environments are outlined here. While no visible flames were detected, this research revealed that auto-combustion existed in the studied area for many years. The occurrence of several amorphous phases, mullite, hematite and many other Al/Fe-minerals formed by high temperature was found. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present work using multi-analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and newmineral creation. It recording huge numbers of rare minerals with alunite, montmorillonite, szmolnockite, halotrichite, coquimbite and copiapite at the BCCRs. The information presented the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing potential hazardous elements (PHEs), such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. Most of the nano-particles and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important impact to environment and subsequently animal and human health. Copyright © 2015 Elsevier Ltd. All rights reserved.
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On the mineral core of ferritin-like proteins: structural and magnetic characterization
NASA Astrophysics Data System (ADS)
García-Prieto, A.; Alonso, J.; Muñoz, D.; Marcano, L.; Abad Díaz de Cerio, A.; Fernández de Luis, R.; Orue, I.; Mathon, O.; Muela, A.; Fdez-Gubieda, M. L.
2015-12-01
It is generally accepted that the mineral core synthesized by ferritin-like proteins consists of a ferric oxy-hydroxide mineral similar to ferrihydrite in the case of horse spleen ferritin (HoSF) and an oxy-hydroxide-phosphate phase in plant and prokaryotic ferritins. The structure reflects a dynamic process of deposition and dissolution, influenced by different biological, chemical and physical variables. In this work we shed light on this matter by combining a structural (High Resolution Transmission Electron Microscopy (HRTEM) and Fe K-edge X-ray Absorption Spectroscopy (XAS)) and a magnetic study of the mineral core biomineralized by horse spleen ferritin (HoSF) and three prokaryotic ferritin-like proteins: bacterial ferritin (FtnA) and bacterioferritin (Bfr) from Escherichia coli and archaeal ferritin (PfFtn) from Pyrococcus furiosus. The prokaryotic ferritin-like proteins have been studied under native conditions and inside the cells for the sake of preserving their natural attributes. They share with HoSF a nanocrystalline structure rather than an amorphous one as has been frequently reported. However, the presence of phosphorus changes drastically the short-range order and magnetic response of the prokaryotic cores with respect to HoSF. The superparamagnetism observed in HoSF is absent in the prokaryotic proteins, which show a pure atomic-like paramagnetic behaviour attributed to phosphorus breaking the Fe-Fe exchange interaction.It is generally accepted that the mineral core synthesized by ferritin-like proteins consists of a ferric oxy-hydroxide mineral similar to ferrihydrite in the case of horse spleen ferritin (HoSF) and an oxy-hydroxide-phosphate phase in plant and prokaryotic ferritins. The structure reflects a dynamic process of deposition and dissolution, influenced by different biological, chemical and physical variables. In this work we shed light on this matter by combining a structural (High Resolution Transmission Electron Microscopy (HRTEM) and Fe K-edge X-ray Absorption Spectroscopy (XAS)) and a magnetic study of the mineral core biomineralized by horse spleen ferritin (HoSF) and three prokaryotic ferritin-like proteins: bacterial ferritin (FtnA) and bacterioferritin (Bfr) from Escherichia coli and archaeal ferritin (PfFtn) from Pyrococcus furiosus. The prokaryotic ferritin-like proteins have been studied under native conditions and inside the cells for the sake of preserving their natural attributes. They share with HoSF a nanocrystalline structure rather than an amorphous one as has been frequently reported. However, the presence of phosphorus changes drastically the short-range order and magnetic response of the prokaryotic cores with respect to HoSF. The superparamagnetism observed in HoSF is absent in the prokaryotic proteins, which show a pure atomic-like paramagnetic behaviour attributed to phosphorus breaking the Fe-Fe exchange interaction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04446d
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Impact of natural organic matter coatings on the microbial reduction of iron oxides
NASA Astrophysics Data System (ADS)
Poggenburg, Christine; Mikutta, Robert; Schippers, Axel; Dohrmann, Reiner; Guggenberger, Georg
2018-03-01
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 the influence of NOM on the stability of Fe-organic associations in soils cannot easily be assessed without considering the composition of the microbial soil community.
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Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model
NASA Astrophysics Data System (ADS)
Bonneville, Steeve; Behrends, Thilo; van Cappellen, Philippe; Hyacinthe, Christelle; Röling, Wilfred F. M.
2006-12-01
A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, Mmax, the attachment constant, KP, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, Km∗, on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.
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The development of Fe-nodules surrounding biological material mediated by microorganisms
NASA Astrophysics Data System (ADS)
Yoshida, Hidekazu; Yamamoto, Koshi; Murakami, Yuki; Katsuta, Nagayoshi; Hayashi, Toru; Naganuma, Takeshi
2008-09-01
Takashikozo is a phenomenon of Quaternary sediments in Japan. They are cylindrical Fe-oxyhydroxide nodules that form as plaques round plant roots, where Fe is preferentially concentrated to develop a solid wall. Structural features suggest that after the roots have decayed, the central space where the roots were situated acts as a flow path for oxidized water. Analysis of microbial 16S rDNA extracted from the nodules identified iron-oxidizing bacteria encrusted round the roots where they are the likely initiators of nodule formation. Direct microscopic observation revealed an accumulation of Fe-oxyhydroxides that fill the pore spaces and is also likely to be linked with the encrusting microbial colonies. Geological history and nanofossil evidence suggest that these Fe-nodules may have been buried at a depth of up to several tens of meters for at least 105 years in reducing Quaternary sediments. Thus Fe-oxyhydroxide nodules that have formed in a geological environment at the interfaces between water and rock by microbial mediation can persist under reducing conditions. If this is the case, the phenomenon is significant as an analogue of post-closure conditions in radioactive waste repositories, since it could influence nuclide migration.
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Potentially bioavailable ferrous iron nanoparticles in glacial sediments
NASA Astrophysics Data System (ADS)
Hawkings, J.; Benning, L. G.; Raiswell, R.; Kaulich, B.; Araki, T.; Abyaneh, M.; Koch-Müller, M.; Stockdale, A.; Tranter, M.; Wadham, J.
2017-12-01
Iron (Fe) is an essential nutrient for marine phytoplankton, the primary producers of the ocean. Despite it being the fourth most abundant element in the Earth's crust, it is highly insoluble, due in part to its rapid oxidation from ferric (Fe2+) to ferrous phases (Fe3+), which often leads to the formation of nanoparticulate iron oxyhydroxide phases1. The insoluble nature of Fe in oxygenated waters means Fe limitation of primary producers is prevalent in 30-50% of the world's oceans, including areas of high biological productivity proximal to significant glacial activity (e.g., the Southern Ocean). Glaciers and ice sheets are a significant source of nanoparticulate Fe, which may be important in sustaining the high productivity observed in the near coastal regions proximal to glacial coverage. The reactivity of particulate iron is poorly understood, despite its importance in the ocean Fe inventory. Here we combined geochemical extractions, high-resolution imaging and spectroscopy to investigate the abundance, morphology and valence state of reactive iron in glacial sediments. Our results document the widespread occurrence of amorphous and Fe(II)-rich nanoparticles in glacial meltwaters and icebergs. Fe(II) is thought to be highly bioavailable in marine environments. We argue that glaciers and ice sheets are therefore able to supply potentially bioavailable Fe(II)-containing nanoparticulate material for downstream ecosystems, including those in a marine setting. The flux of bioavailable particulate iron from Arctic glaciers may increase as rising air temperatures lead to higher meltwater export.
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Zhou, Yan-Li; Yang, Ying; Chen, Mo; Zhao, Zhi-Wei; Jiang, He-Long
2014-05-01
Effects of iron oxide amendment into freshwater sediments on performance of sediment microbial fuel cell (SMFC) were investigated. It was found that amending amorphous bulk ferric oxyhydroxide, and crystalline goethite and magnetite did not affect SMFC operation. However, amendment of the mixed solution including soluble ferric citrate and colloidal iron oxyhydroxide, stably improved SMFC performance with voltage outputs up to threefolds higher than those without amendment. The enhanced voltage production corresponded to lower anode potential, but was not related to organic matter removal in sediments. Further experiments demonstrated that colloidal iron oxyhydroxide instead of soluble ferric iron played an important role in voltage production through maintaining high-concentration ferrous iron in pore water of sediments as electron shuttle and for chemical oxidation on the anode. Thus, colloidal iron oxyhydroxide amendment was a promising strategy to improve power production from SMFC employed in sediments especially with low content of organic matters. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Klem, Michael T; Mosolf, Jesse; Young, Mark; Douglas, Trevor
2008-04-07
The Fe storage protein ferritin was used as a size-constrained reaction vessel for the photoreduction and reoxidation of complexed Eu, Fe, and Ti precursors for the formation of oxyhydroxide nanoparticles. The resultant materials were characterized by dynamic light scattering, gel electrophoresis, UV-vis spectroscopy, and transmission electron microscopy. The photoreduction and reoxidation process is inspired by biological sequestration mechanisms observed in some marine siderophore systems.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Swanner, E. D.; Bayer, T.; Wu, W.
In this study, we couple iron isotope analysis to microscopic and mineralogical investigation of iron speciation during circumneutral Fe(II) oxidation and Fe(III) precipitation with photosynthetically produced oxygen. In the presence of the cyanobacterium Synechococcus PCC 7002, aqueous Fe(II) (Fe(II) aq) is oxidized and precipitated as amorphous Fe(III) oxyhydroxide minerals (iron precipitates, Fe ppt), with distinct isotopic fractionation (ε 56Fe) values determined from fitting the δ 56Fe(II) aq (1.79‰ and 2.15‰) and the δ 56Fe ppt (2.44‰ and 2.98‰) data trends from two replicate experiments. Additional Fe(II) and Fe(III) phases were detected using microscopy and chemical extractions and likely represent Fe(II)more » and Fe(III) sorbed to minerals and cells. The iron desorbed with sodium acetate (FeNaAc) yielded heavier δ 56Fe compositions than Fe(II) aq. Modeling of the fractionation during Fe(III) sorption to cells and Fe(II) sorption to Feppt, combined with equilibration of sorbed iron and with Fe(II) aq using published fractionation factors, is consistent with our resulting δ 56FeNaAc. The δ 56Fe ppt data trend is inconsistent with complete equilibrium exchange with Fe(II)aq. Because of this and our detection of microbially excreted organics (e.g., exopolysaccharides) coating Feppt in our microscopic analysis, we suggest that electron and atom exchange is partially suppressed in this system by biologically produced organics. These results indicate that cyanobacteria influence the fate and composition of iron in sunlit environments via their role in Fe(II) oxidation through O 2 production, the capacity of their cell surfaces to sorb iron, and the interaction of secreted organics with Fe(III) minerals.« less
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Hein, J.R.; Schulz, M.S.; Dunham, R.E.; Stern, R.J.; Bloomer, S.H.
2008-01-01
Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 ?? and 7 ?? manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean-8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along, the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms. Copyright 2008 by the American Geophysical Union.
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NASA Astrophysics Data System (ADS)
Hein, James R.; Schulz, Marjorie S.; Dunham, Rachel E.; Stern, Robert J.; Bloomer, Sherman H.
2008-08-01
Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 Å and 7 Å manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean 8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms.
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Newly recognized hosts for uranium in the Hanford Site vadose zone
Stubbs, J.E.; Veblen, L.A.; Elbert, D.C.; Zachara, J.M.; Davis, J.A.; Veblen, D.R.
2009-01-01
Uranium contaminated sediments from the U.S. Department of Energy's Hanford Site have been investigated using electron microscopy. Six classes of solid hosts for uranium were identified. Preliminary sediment characterization was carried out using optical petrography, and electron microprobe analysis (EMPA) was used to locate materials that host uranium. All of the hosts are fine-grained and intergrown with other materials at spatial scales smaller than the analytical volume of the electron microprobe. A focused ion beam (FIB) was used to prepare electron-transparent specimens of each host for the transmission electron microscope (TEM). The hosts were identified as: (1) metatorbernite [Cu(UO2)2(PO4)2??8H2O]; (2) coatings on sediment clasts comprised mainly of phyllosilicates; (3) an amorphous zirconium (oxyhydr)oxide found in clast coatings; (4) amorphous and poorly crystalline materials that line voids within basalt lithic fragments; (5) amorphous palagonite surrounding fragments of basaltic glass; and (6) Fe- and Mn-oxides. These findings demonstrate the effectiveness of combining EMPA, FIB, and TEM to identify solid-phase contaminant hosts. Furthermore, they highlight the complexity of U geochemistry in the Hanford vadose zone, and illustrate the importance of microscopic transport in controlling the fate of contaminant metals in the environment. ?? 2008 Elsevier Ltd.
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Wang, Tanyuan; Nam, Gyutae; Jin, Yue; Wang, Xingyu; Ren, Pengju; Kim, Min Gyu; Liang, Jiashun; Wen, Xiaodong; Jang, Haeseong; Han, Jiantao; Huang, Yunhui; Li, Qing; Cho, Jaephil
2018-05-21
A facile H 2 O 2 oxidation treatment to tune the properties of metal disulfides for oxygen evolution reaction (OER) activity enhancement is introduced. With this method, the degree of oxidation can be readily controlled and the effect of surface S residues in the resulted metal (oxy)hydroxides for the OER is revealed for the first time. The developed NiFe (oxy)hydroxide catalyst with residual S demonstrates an extraordinarily low OER overpotential of 190 mV at the current density of 10 mA cm -2 after coupling with carbon nanotubes, and outstanding performance in Zn-air battery tests. Theoretical calculation suggests that the surface S residues can significantly reduce the adsorption free energy difference between O* and OH* intermediates on the Fe sites, which should account for the high OER activity of NiFe (oxy)hydroxide catalysts. This work provides significant insight regarding the effect of surface heteroatom residues in OER electrocatalysis and offers a new strategy to design high-performance and cost-efficient OER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Zhou, Qiong; Albert, Olga; Deng, Hua; Yu, Xiao-Long; Cao, Yang; Li, Jian-Bao; Huang, Xin
2012-12-01
This paper investigated the effects of five kinds of Au surfaces terminated with and without functional groups on the crystallization of ferric oxides/oxyhydroxides in the suspension condition. Self-assembled monolayers (SAMs) were used to create hydroxyl (-OH), carboxyl (-COOH), amine (-NH2) and methyl (-CH3) functionalized surfaces, which proved to be of the same surface density. The immersion time of substrates in the Fe(OH)3 suspension was divided into two time portions. During the first period of 2 h, few ferric oxide/oxyhydroxide was deposited except that ɛ-Fe2O3 was detected on -NH2 surface. Crystallization for 10 h evidenced more kinds of iron compounds on the functional surfaces. Goethite and maghemite were noticed on four functional surfaces, and maghemite also grew on Au surface. Deposition of ɛ-Fe2O3 was found on -OH surface, while the growth of orthorhombic and hexagon FeOOH were indicated on -NH2 surface. Considering the wide existence of iron compounds in nature, our investigation is a precedent work to the study of iron biomineralization in the suspension area.
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Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.
2015-01-01
To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.
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Jones, E.J.P.; Voytek, M.A.; Lorah, M.M.
2004-01-01
1,1,2,2-Tetrachloroethane (TeCA) contaminated groundwater at the Aberdeen Proving Ground discharges through an anaerobic wetland in West Branch Canal Creek, MD, where dechlorination occurred. Two microbially mediated pathways, dichloroelimination and hydrogenolysis, account for most of the TeCA degradation at this site. The dichloroelimination pathways led to the formation of vinyl chloride (VC), a recalcitrant carcinogen of great concern. The effect of adding Fe(III) to TeCA-amended microcosms of wetland sediment was studied. Differences were identified in the TeCA degradation pathway between microcosms treated with amorphous ferric oxyhydroxide (AFO-treated) and untreated (no AFO) microcosms. TeCA degradation was accompanied by a lower accumulation of VC in AFO-treated microcosms than no AFO microcosms. The microcosm incubations and subsequent experiments with the microcosm materials showed that AFO treatment resulted in lower production of VC by shifting TeCA degradation from dichloroelimination pathways to production of a greater proportion of chlorinated ethane products, and decreasing the microbial capability to produce VC from 1,2-dichloroethylene. VC degradation was not stimulated in the presence of Fe(III). Rather, VC degradation occurred readily under methanogenic conditions and was inhibited under Fe(III)-reducing conditions.
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NASA Astrophysics Data System (ADS)
Pierre-Louis, Andro-Marc
With the benefits of an ever increasing advance of industrialization around the globe come formidable environmental problems. Three environmental problems that have relevance to the research described in this thesis are the 1) buildup of atmospheric CO2 gas through the burning of fossil fuels, 2) eutrophication of aquatic systems, and 3) the acidification of environments from acid mine drainage (AMD) resulting from coal-mining activities. In particular research is presented in this thesis that investigated the surface chemistry of CO2 and phosphate (PO43-) on a suite of environmentally relevant iron oxyhydroxide materials and the chemistry of phospholipid molecules on environmentally relevant iron sulfide surfaces to suppress AMD. To develop a microscopic understanding of the surface chemistry of the different systems, an array of experimental and computational techniques were used in the research. Techniques included X-ray photoelectron spectroscopy, atomic adsorption, X-ray diffraction, scanning transmission microscopy with electron dispersive X-ray spectroscopy (STEM/EDS), ion chromatography (IC), and attenuated total reflectance Fourier transform Infrared (ATR-FTIR). Results from the latter technique were interpreted with the aid of density function theory (DFT) calculations. Iron oxyhydroxides, which consisted of ferrihydrite (FeOOH), goethite (α-FeOOH), ferrimagnetic ferrihydrite (FerriFh), and aluminum-doped iron oxyhydroxide (content from 0-100 mol%) were synthesized and studied before and after exposure to gaseous CO2, CO32-, and PO43- species. FeOOH and mixed Al/Fe oxyhydroxide surfaces showed high affinities for the formation of carbonate and bicarbonate species upon exposure to gaseous CO2. Within the Al/Fe oxyhydroxide circumstance, a low Al level of incorporation in the iron oxyhydroxide structure caused a slight increase in surface area and increase in the amount of oxyanion (e.g., CO32- or PO43-) adsorption up to an Al level of 30 mol%. Significant changes were observed in the binding geometry of the adsorbed complexes on the Al/Fe mineral compared to single phase α-FeOOH, AlOOH, and FeOOH surfaces. ATR-FTIR results combined with vibrational frequency (DFT) calculations suggested the formation of multiple phosphate surface complexes via a variety of configurations such as inner-sphere/outer-sphere bidentate, monodentate depending on the solution pH and the Al mol% substituted into the Fe-oxyhydroxide. Studies investigated the adsorption of CO2 on FerriFh and compared those results to CO2 on ferrihydrite. The CO2 pressures used in these particular studies ranged from 1 to 57.8 bars. It is found that citrate bound species, resulting from the synthesis conditions used to make FerriFh, blocked surface sites for the formation of carbonate and bicarbonate species on the magnetic FerriFh and ferrihydrite oxyhydroxide minerals upon CO2(gas) exposure. A bicarbonate or bent-CO 2 like species (~1220 cm-1) formed at lower CO2 pressures (≤ 3.5 bars) but was absent at the higher pressures. Additional studies investigated the adsorption of various phospholipid molecules on pyrite, and iron sulfide with FeS2 stoichiometry. These studies were focused on suppressing the oxidative decomposition of pyrite to sulfuric acid, the root cause of AMD. Batch and column studies were employed to investigate the ability of phospholipids to reduce AMD over an extended period of time (up to 3 years). In studies that used actual coal mining refuse, which contained significant amount of pyrite, it was shown that the rate of acid production from pyrite decomposition could be reduced by as much as 70% due to the presence of surface bound phospholipid. Assembly of the phospholipid into a bilayer motif on the sulfide surface was hypothesized to form a hydrophobic barrier that kept dissolved O2 and bacteria from facilitating the oxidation of FeS2. Column experiments showed that when water at pH 7 was flowed over the coal mining waste, the effluent had a pH close to 3. In contrast when water at pH 7 was flowed over the pyrite containing waste, which was pretreated with lipid, the effluent had a pH closer to 7, and the total amount of Fe (Fe2+/Fe3+) and SO42- in the effluent waters was also reduced relative to the untreated pyrite containing waste circumstance. These studies showed that the application of phospholipid to pyrite containing coal mining waste could potentially be an environmentally friendly remediation technique.
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Iron cycling under oscillatory redox conditions: from observations to processes
NASA Astrophysics Data System (ADS)
Meile, C. D.; Chen, C.; Barcellos, D.; Wilmoth, J.; Thompson, A.
2017-12-01
Fe oxyhydroxides play a critical role in soils through their role as structural entities, their high sorption capacity, their role as terminal electron acceptors in the respiration of organic matter, as well as their potential to affect the reactivity of that organic matter. In soils that undergo repeated fluctuations in O2 concentrations, soil iron undergoes transformations between reduced and oxidized forms. The rate of Fe(II) oxidation can govern the nature of Fe(III) oxyhydroxides formed, and hence can affect rates of OC mineralization under suboxic conditions. But it remains unclear if this same behavior occurs in soils, where Fe(II) is mainly present as surface complexes. We documented the impact of such redox oscillations on iron cycling through targeted experiments, in which the magnitude and frequency of redox oscillations were varied systematically on soils from the Luquillo Critical Zone Observatory, Puerto Rico. Our observations demonstrated that higher O2 concentrations led to a faster Fe(II) oxidation and resulted in less crystalline Fe(III)-oxyhydroxides than lower O2 concentrations. We further studied the dynamics of iron phases by amending soil slurries with isotopically-labeled 57Fe(II) and developed a numerical model to quantify the individual processes. Our model showed a higher rate of Fe(III) reduction and increased sorption capacity following the oxidation of Fe(II) at high O2 levels than at low O2 levels, and revealed rapid Fe atom exchange between solution and solid phase. Concurrent measurements of CO2 in our oscillation experiments further illustrated the importance O2 fluctuations on coupled Fe-C dynamics.
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NASA Astrophysics Data System (ADS)
Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.
2014-12-01
The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.
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Templating Growth of a Pseudomorphic Lepidocrocite Microshell at the Calcite–Water Interface
Yuan, Ke; Lee, Sang Soo; Wang, Jun; ...
2018-01-05
The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104)more » surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.« less
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NASA Astrophysics Data System (ADS)
Kretzschmar, R.; Kiczka, M.; Wiederhold, J. G.; Voegelin, A.; Kraemer, S.; Bourdon, B.
2010-12-01
Iron (Fe) is not only an essential element for almost all organisms, but is also involved in many biogeochemical processes including silicate weathering and soil formation. The aim of this study was to gain a better understanding of Fe isotope fractionation during initial silicate weathering and soil formation processes. Therefore, we investigated changes in Fe speciation and Fe isotope signatures in total soils and selected Fe pools along a weathering chronosequence within an Alpine glacier forefield on granite. The sampling sites along the dated chronosequence were deglaciated since up to 150 years, and we included two additional sites which were ice-free since several thousands of years. Changes in Fe speciation were investigated using Fe K-edge X-ray absorption spectroscopy (XAS) and also qualitatively documented by optical microscopy of soil thin sections. Iron in the unweathered rock was mainly present as structural Fe in biotite, with smaller amounts in chlorite, epidote, and magnetite. Within 150 years of deglaciation, the fraction of Fe(III) relative to total Fe increased from 34 to 53%, clearly documenting oxidation of Fe(II) in primary phyllosilicates. After 100 years of deglaciation, secondary Fe(III)-oxyhydroxides were detected by XAS and were also clearly evident in soil thin sections. Elemental analysis and Fe isotope analysis of particle size fractions by MC-ICP-MS showed that the clay fractions were significantly enriched in Fe and their δ56Fe signatures were up to 0.35‰ lower than those of the bulk soils (<2 mm). In addition, the hydroxylamine-hydrochloride extractable Fe pool (1 M HA-HCl in 25% acetic acid, pH 1.5), representing mainly poorly-crystalline Fe(III)-oxyhydroxides, increased with time of deglaciation and also had a significantly (by up to 0.7‰) lighter δ56Fe signature than the respective bulk soils. Thus, our data show that weathering of primary silicates, mainly biotite and chlorite, preferentially releases light Fe isotopes during oxidative weathering, which are subsequently enriched in secondary Fe(III)-oxyhydroxides with a rather constant isotopic offset of -0.7‰ in δ56Fe relative to the bulk soils. These findings are consistent with previous laboratory experiments on silicate weathering by proton- and ligand-promoted dissolution. The data suggest a kinetic isotope effect during Fe release from primary silicates, combined with quantitative oxidation and precipitation of Fe(III) as poorly-crystalline oxyhydroxides. Analysis of plants collected along the chronosequence revealed additional fractionation towards light Fe isotopes, but the plant contribution to total Fe cycling in this young ecosystem was still minor.
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Formation of Deep Sea Umber Deposits Linked to Microbial Metal Oxidation at the South Atlantic Ridge
NASA Astrophysics Data System (ADS)
Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao
2015-04-01
Umber deposits are important metalliferous deposits, which occur in off-axis half-graben structures at ancient and modern ocean floor. The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biochemical mechanisms involved to the precipitation of Mn oxides and co-precipitation of Fe oxyhydroxides and Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data suggest that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic Fe(II)-oxidizing bacteria, which constitute a trophic base that may support the activities of heterotrophic Mn(II)-oxidizing bacteria. The biological origin of umber deposits underscore the importance of geomicrobiologcial interaction in triggering the formation of deep-sea deposits, with important implications for the generation of submarine Mn deposits and crusts.
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NASA Astrophysics Data System (ADS)
Prikryl, James D.; Pickett, David A.; Murphy, William M.; Pearcy, English C.
1997-04-01
Oxidation of pyrite at the Nopal I uranium deposit, Peña Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity {234U}/{238U} activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess 234U. Systematic decreases in {234U}/{238U} activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from 234U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess 234U.
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Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.
2012-01-01
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.
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Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Billstrom, Kjell; Kamenov, George D.; Shanks, Wayne C.; Stummeyer, Jens
2011-01-01
Dredging along the west wall of the core complex at 12°50′N Mid-Atlantic Ridge sampled a number of black oxyhydroxide crusts and breccias cemented by black and dark brown oxyhydroxide matrix. Black crusts found on top of basalt clasts (rubble) are mainly composed of Mn-oxides (birnessite, 10-Å manganates) with thin films of nontronite and X-ray amorphous FeOOH on their surfaces. Their chemical composition (low trace- and rare earth-element contents, high Li and Ag concentrations, rare earth element distribution patterns with negative both Ce and Eu anomalies), Sr–Nd–Pb-isotope systematic and O-isotope data suggest low-temperature (~ 20 °C) hydrothermal deposition from a diffuse vent area on the seafloor. Mineralogical, petrographic and geochemical investigations of the breccias showed the rock clasts were hydrothermally altered fragments of MORBs. Despite the substantial mineralogical changes caused by the alteration the Sr–Nd–Pb-isotope ratios have not been significantly affected by this process. The basalt clasts are cemented by dark brown and black matrix. Dark brown cement exhibits geochemical features (very low trace- and rare earth- element contents, high U concentration, rare earth element distribution pattern with high positive Eu anomaly) and Nd–Pb-isotope systematics (similar to that of MORB) suggesting that the precursor was a primary, high-temperature Fe-sulfide, which was eventually altered to goethite at ambient seawater conditions. The data presented in this work points towards the possible existence of high- and low-temperature hydrothermal activity at the west wall of the core complex at 12°50′N Mid-Atlantic Ridge. Tectonic setting at the site implies that the proposed hydrothermal field is possibly ultramafic-hosted.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Combes, J.M.; Manceau, A.; Calas, G.
1989-03-01
X-ray absorption spectroscopy (XAS) was used to follow the evolution of local structural environments around ferric ions during the formation of ferric hydrous oxide gels from 1 M chloride and 0.1 M nitrate solutions. Fe K-XANES and EXAFS confirm that ferric ions remain 6-fold coordinated during this evolution. With increasing OH availability in the solution, Cl{sup {minus}} anions tend gradually to be exchanged for (O, OH, OH{sub 2}) ligands. Below OH/Fe = 1, no structural order is detected beyond the first coordination sphere. Above this ratio, two Fe-Fe distances at 3.05 {angstrom} and 3.44 {angstrom} are observed and correspond tomore » the presence of edge- and vertex-sharing Fe-octahedra. XAS results show that ferric gels and highly polymerized aqueous species are short-range ordered. The main contribution to disorder in the gels arises from the small size of coherently scattering domains also responsible for their X-ray amorphous character. From the initial to the final stage of hydrolysis, particles possess a nearly spherical shape with a minimum average diameter ranging from 10-30 {angstrom} for polymers formed from chloride and nitrate solutions. As polymerization proceeds, the local order extends to several tens of angstroms and the particle structures becomes progressively closer to that of akaganeite ({beta}-FeOOH) or goethite ({alpha}-FeOOH). This local structure is distinct from that of the lepidocrocite ({gamma}-FeOOH)-like structure of ferric gels precipitated after oxidation of divalent Fe solutions. The growth of the crystalline Fe-oxyhydroxides from gels takes place by the progressive long-range ordering in the ferric polymers without modifying the short-range order around Fe.« less
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Iron-rich colloids as carriers of phosphorus in streams: A field-flow fractionation study.
Baken, Stijn; Regelink, Inge C; Comans, Rob N J; Smolders, Erik; Koopmans, Gerwin F
2016-08-01
Colloidal phosphorus (P) may represent an important fraction of the P in natural waters, but these colloids remain poorly characterized. In this work, we demonstrate the applicability of asymmetric flow field-flow fractionation (AF4) coupled to high resolution ICP-MS for the characterization of low concentrations of P-bearing colloids. Colloids from five streams draining catchments with contrasting properties were characterized by AF4-ICP-MS and by membrane filtration. All streams contain free humic substances (2-3 nm) and Fe-bearing colloids (3-1200 nm). Two soft water streams contain primary Fe oxyhydroxide-humic nanoparticles (3-6 nm) and aggregates thereof (up to 150 nm). In contrast, three harder water streams contain larger aggregates (40-1200 nm) which consist of diverse associations between Fe oxyhydroxides, humic substances, clay minerals, and possibly ferric phosphate minerals. Despite the diversity of colloids encountered in these contrasting streams, P is in most of the samples predominantly associated with Fe-bearing colloids (mostly Fe oxyhydroxides) at molar P:Fe ratios between 0.02 and 1.5. The molar P:Fe ratio of the waters explains the partitioning of P between colloids and truly dissolved species. Waters with a high P:Fe ratio predominantly contain truly dissolved species because the Fe-rich colloids are saturated with P, whereas waters with a low P:Fe ratio mostly contain colloidal P species. Overall, AF4-ICP-MS is a suitable technique to characterize the diverse P-binding colloids in natural waters. Such colloids may increase the mobility or decrease the bioavailability of P, and they therefore need to be considered when addressing the transport and environmental effects of P in catchments. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Leiviskä, Tiina; Khalid, Muhammad Kamran; Sarpola, Arja; Tanskanen, Juha
2017-04-01
This study investigated the removal of vanadium from real industrial wastewater by using six iron materials: commercial iron sorbent (CFH-12), commercial mineral sorbent (AQM), blast furnace sludge (BFS), steel converter sludge (SCS), ferrochrome slag (FeCr) and slag from a steel foundry (OKTO). Batch tests revealed that CFH-12 (ferric oxyhydroxide) removed vanadium most efficiently, which was explained by its high iron content and the amorphous form of the iron, and that the sorption followed the Langmuir isotherm. With a dosage of 10 g/l and an initial vanadium concentration of 58.2 mg/l, 91-94% removal rates for vanadium were achieved in the studied pH range (3-9). Other sorbents showed significantly lower efficiency than CFH-12, with the exception of BFS at acidic pH (93%). Based on the batch test results, CFH-12 was selected for a pilot study made on site. The pilot study demonstrated the feasibility of CFH-12 to remove vanadium at high temperature (80 °C) from concentrated industrial wastewater with fluctuating water quality (vanadium concentration varied from 51 to 83 mg/l, pH about 9 (at 25 °C)). Leaching of impurities (mainly S, Ca, Mg and K) into the effluent occurred during the first day, but subsequently good quality effluent was produced (e.g. <0.1 mg/l V). During the pilot study, the amorphous iron material of CFH-12 was crystallized into a hematite-like phase (Fe 1.67 H 0.99 O 3 ), and goethite (FeO(OH)) with a higher average pore diameter, probably due to the hot process conditions to which CFH-12 was exposed for over five days. Copyright © 2016 Elsevier Ltd. All rights reserved.
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The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tresintsi, S.; Simeonidis, K., E-mail: ksime@physics.auth.gr; Department of Mechanical Engineering, University of Thessaly, 38334 Volos
2014-05-01
This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted inmore » distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.« less
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Pratt, C; Shilton, A
2010-01-01
Active filtration, where effluent is passed through a reactive substrate such as steel slag, offers a simple and cost-effective option for removing phosphorus (P) from effluent. This work summarises a series of studies that focused on the world's only full-scale active slag filter operated through to exhaustion. The filter achieved 75% P-removal during its first 5 years, reaching a retention capacity of 1.23 g P/kg slag but then its performance sharply declined. Scanning electron microscopy, X-ray diffraction, X-ray fluorescence, and chemical extractions revealed that P sequestration was primarily achieved via adsorption onto iron (Fe) oxyhydroxides on the slag's surface. It was concluded that batch equilibrium tests, whose use has been repeatedly proposed in the literature, cannot be used as an accurate predictor of filter adsorption capacity because Fe oxyhydroxides form via chemical weathering in the field, and laboratory tests don't account for this. Research into how chemical conditions affect slag's P retention capacity demonstrated that near-neutral pH and high redox are optimal for Fe oxyhydroxide stability and overall filter performance. However, as Fe oxyhydroxide sites fill up, removal capacity becomes exhausted. Attempts to regenerate P removal efficiency using physical techniques proved ineffective contrary to dogma in the literature. Based on the newly-developed understanding of the mechanisms of P removal, chemical regeneration techniques were investigated and were shown to strip large quantities of P from filter adsorption sites leading to a regenerated P removal efficiency. This raises the prospect of developing a breakthrough technology that can repeatedly remove and recover P from effluent.
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NASA Technical Reports Server (NTRS)
Golden, D. C.; Ming, Douglas W.; Morris, Richard V.; Mertzman, A.
2006-01-01
Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system and (3) single-step hydrothermal batch treatment approximating a "closed system." In acid fog experiments, Al, Fe, and Ca sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg and Ca sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg and Ca sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. Based upon our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.
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Jones, Elizabeth; Voytek, Mary; Lorah, Michelle
2004-01-01
1,1,2,2-Tetrachloroethane (TeCA) contaminated groundwater at the Aberdeen Proving Ground discharges through an anaerobic wetland in West Branch Canal Creek (MD), where dechlorination occurs. Two microbially mediated pathways, dichloroelimination and hydrogenolysis, account for most of the TeCA degradation at this site. The dichloroelimination pathways lead to the formation of vinyl chloride (VC), a recalcitrant carcinogen of great concern. The goal of this investigation was to determine whether microbially-available Fe(III) in the wetland surface sediment influenced the fate of TeCA and its daughter products. Differences were identified in the TeCA degradation pathway between microcosms treated with amorphous ferric oxyhydroxide (AFO-treated) and untreated (no AFO) microcosms. TeCA degradation was accompanied by a lower accumulation of VC in AFO-treated microcosms than untreated microcosms. The microcosm incubations and subsequent experiments with the microcosm materials showed that AFO treatment resulted in lower production of VC by (1) shifting TeCA degradation from dichloroelimination pathways to production of a greater proportion of chlorinated ethane products, and (2) decreasing the microbial capability to produce VC from 1,2-dichloroethene (DCE). VC degradation was not stimulated in the presence of Fe(III). Rather, VC degradation occurred readily under methanogenic conditions and was inhibited under Fe(III)-reducing conditions.
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NASA Astrophysics Data System (ADS)
Koukina, S. E.; Vetrov, A. A.
2013-09-01
This study focuses on sediments from small restricted exchange environments along the Karelian shore of Kandalaksha Bay (White Sea, Russian Arctic), which are known as separating basins and are characterised by contrasting oxidising conditions within the water column and the occurrence of anoxia. In the basins that were studied, no significant contamination by trace heavy metals (Pb, Cu, Zn and Cr, in particular) was detected. The comparative study of the two most bioavailable metal forms, namely, labile (acid soluble) and organically bound (alkali soluble) forms, indicated that acetic acid and sodium pyrophosphate released 3-11% and 2-12%, respectively, of the total metal content from sediments. The most bioavailable parts of metals are weakly bound to organic matter and, to a greater extent, associated with easily soluble amorphous Fe-oxides. Among the studied elements, most of the bioavailable Zn and Cu was most likely bound to organic substances, whereas bioavailable Cr and Mn were controlled to a greater extent by the formation of Fe-oxyhydroxide. The elements studied could be arranged in the following decreasing order of average potential bioavailability: Cu > Zn > Mn > Fe > Cr > Pb. In the separating basins, the relative proportion of labile bioavailable metals is enhanced in relation to the neighbouring open coastal sea.
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NASA Astrophysics Data System (ADS)
Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.
2018-05-01
Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.
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NASA Astrophysics Data System (ADS)
Nath, Bibhash; Chakraborty, Sudipta; Burnol, André; Stüben, Doris; Chatterjee, Debashis; Charlet, Laurent
2009-01-01
SummaryGroundwater and aquifer materials have been characterized geochemically at a field site located in the Chakdaha municipality of West Bengal, India. Sorption experiments were also carried out on a sandy aquifer material to understand the mobility of arsenic (As) in the sub-surface environments. The result shows that the areas associated with high groundwater As (mean: 1.8 μM) is typically associated with low Eh (mean: -129 mV), and high Fe (mean: 0.11 mM), where Fe 2+/Fe(OH) 3 couple is controlling groundwater redox potential. Analysis of the aquifer material total concentrations showed the dominance of As (range: 8.9-22 mg kg -1), Fe (range: 3.0-9.7% as Fe 2O 3) and Mn (range: 0.05-0.18% as MnO) in the silt-/clay-rich sediments; whereas fine-/medium-sand rich sediment contains considerably lower amount of As (<8.1 mg kg -1), Fe (range: 1.6-3.9% as Fe 2O 3) and Mn (range: 0.02-0.08% as MnO). The acid extractable As do not correlate with ascorbate extractable Fe-oxyhydroxide, however Fe-oxyhydroxide is generally high in the sediments from low groundwater As areas. Chemical speciation computations indicated Fe(II), Ca(II), Mg(II) and Mn(II) to be at equilibrium (with respect to calcite, dolomite and rhodochrosite) or slightly over-saturated (with respect to siderite). These carbonate minerals may therefore participate to the As immobilization. The measured total organic carbon (˜1%) and groundwater temperature (26-32 °C) coupled with sorption studies strongly favors microbially mediated Fe(III)-oxyhydroxide reduction as the dominant mechanism for the release of As in the groundwater. Oscillations of As, Mn and Fe concentrations with depth reflected pCO 2 oscillations consecutive to microbial respiration intensity.
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NASA Astrophysics Data System (ADS)
Censi, P.; Raso, M.; Yechieli, Y.; Ginat, H.; Saiano, F.; Zuddas, P.; Brusca, L.; D'Alessandro, W.; Inguaggiato, C.
2017-03-01
Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.
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Arce, Guillermo; Montecinos, Mauricio; Guerra, Paula; Escauriaza, Cristian; Coquery, Marina; Pastén, Pablo
2017-08-01
Acid drainage (AD) is an important environmental concern that impacts water quality. The formation of reactive Fe and Al oxyhydroxides during the neutralization of AD at river confluences is a natural attenuation process. Although it is known that organic matter (OM) can affect the aggregation of Fe and Al oxyhydroxides and the sorption of As onto their surfaces, the role of OM during the neutralization of AD at river confluences has not been studied. Field and experimental approaches were used to understand this role, using the Azufre River (pH 2) - Caracarani River (pH 8.6) confluence (northern Chile) as model system. Field measurements of organic carbon revealed a 10-15% loss of OM downstream the confluence, which was attributed to associations with Fe and Al oxyhydroxides that settle in the river bed. Laboratory mixtures of AD water with synthetic Caracarani waters under varying conditions of pH, concentration and type of OM revealed that OM promoted the aggregation of Fe oxyhydroxides without reducing As sorption, enhancing the removal of As at slightly acidic conditions (pH ∼4.5). At acidic conditions (pH ∼3), aggregation of OM - metal complexes at high OM concentrations could become the main removal mechanism. One type of OM promoted bimodal particle size distributions with larger mean sizes, possibly increasing the settling velocity of aggregates. This work contributes to a better understanding of the role of OM in AD affected basins, showing that the presence of OM during processes of neutralization of AD can enhance the removal of toxic elements. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Darab, J.G.; Linehan, J.C.; Matson, D.W.
1993-06-01
Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.
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Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Darab, J.G.; Linehan, J.C.; Matson, D.W.
1993-06-01
Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.
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NASA Astrophysics Data System (ADS)
Virtasalo, Joonas J.; Laitala, Jaakko J.; Lahtinen, Raimo; Whitehouse, Martin J.
2015-12-01
The Paleoproterozoic, 2.0-1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi-Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δ34S and δ56Fe values of the bedded pyrite (median δ34S = - 10.3 ‰ and δ56Fe = - 0.79 ‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δ34S = - 3.3 ‰ and δ56Fe = - 1.6 ‰) indicates microbial iron reduction. The Fe (oxyhydr)oxide aggregates were transported in muddy debris flows to the distal euxinic seafloor. Their Fe (oxyhydr)oxide matrix was replaced by pyrite (median δ34S = + 5.8 ‰ and δ56Fe = + 0.81 ‰) at shallow sediment depths with 34S and 56Fe-enriched porewater. Wavy-crinkly laminae of possible microbial origin developed on the euxinic seafloor during low sedimentation. These results indicate episodic deposition at seasonal to multiannual time scales. δ34S and δ56Fe values in the studied Fe-sulfides provide evidence of microbial isotope fractionation processes and syndepositional and early-diagenetic origin, finding no support for the previously proposed local hydrothermal activity in the Talvivaara mudstones.
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Sharif, M.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Kresse, T.M.; Fazio, J.A.
2008-01-01
Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.
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Control of arsenic mobilization in paddy soils by manganese and iron oxides.
Xu, Xiaowei; Chen, Chuan; Wang, Peng; Kretzschmar, Ruben; Zhao, Fang-Jie
2017-12-01
Reductive mobilization of arsenic (As) in paddy soils under flooded conditions is an important reason for the relatively high accumulation of As in rice, posing a risk to food safety and human health. The extent of As mobilization varies widely among paddy soils, but the reasons are not well understood. In this study, we investigated As mobilization in six As-contaminated paddy soils (total As ranging from 73 to 122 mg kg -1 ) in flooded incubation and pot experiments. Arsenic speciation in the solution and solid phases were determined. The magnitude of As mobilization into the porewater varied by > 100 times among the six soils. Porewater As concentration correlated closely with the concentration of oxalate-extractable As, suggesting that As associated with amorphous iron (oxyhydr)oxides represents the potentially mobilizable pool of As under flooded conditions. Soil containing a high level of manganese oxides showed the lowest As mobilization, likely because Mn oxides retard As mobilization by slowing down the drop of redox potential upon soil flooding and maintaining a higher arsenate to arsenite ratio in the solid and solution phases. Additions of a synthetic Mn oxide (hausmannite) to two paddy soils increased arsenite oxidation, decreased As mobilization into the porewater and decreased As concentrations in rice grain and straw. Consistent with previous studies using simplified model systems or pure mineral phases, the present study shows that Mn oxides and amorphous Fe (oxyhydr)oxides are important factors controlling reductive As mobilization in As-contaminated paddy soils. In addition, this study also suggests a potential mitigation strategy using exogenous Mn oxides to decrease As uptake by rice in paddy soils containing low levels of indigenous Mn oxides, although further work is needed to verify its efficacy and possible secondary effects under field conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Bligh, Mark W; Maheshwari, Pradeep; David Waite, T
2017-11-01
Iron salts are routinely dosed in wastewater treatment as a means of achieving effluent phosphorous concentration goals. The iron oxides that result from addition of iron salts partake in various reactions, including reductive dissolution and phosphate adsorption. The reactivity of these oxides is controlled by the conditions of formation and the processes, such as aggregation, that lead to a reduction in accessible surface sites following formation. The presence of organic compounds is expected to significantly impact these processes in a number of ways. In this study, amorphous ferric oxide (AFO) reactivity and aging was investigated following the addition of ferric iron (Fe(III)) to three solution systems: two synthetic buffered systems, either containing no organic or containing alginate, and a supernatant system containing soluble microbial products (SMPs) sourced from a membrane bioreactor (MBR). Reactivity of the Fe(III) phases in these systems at various times (1-60 min) following Fe(III) addition was quantified by determining the rate constants for ascorbate-mediated reductive dissolution over short (5 min) and long (60 min) dissolution periods and for a range (0.5-10 mM) of ascorbate concentrations. AFO particle size was monitored using dynamic light scattering during the aging and dissolution periods. In the presence of alginate, AFO particles appeared to be stabilized against aggregation. However, aging in the alginate system was remarkably similar to the inorganic system where aging is associated with aggregation. An aging mechanism involving restructuring within the alginate-AFO assemblage was proposed. In the presence of SMPs, a greater diversity of Fe(III) phases was evident with both a small labile pool of organically complexed Fe(III) and a polydisperse population of stabilized AFO particles present. The prevalence of low molecular weight organic molecules facilitated stabilization of the Fe(III) oxyhydroxides formed but subsequent aging observed in the alginate system did not occur. The reactivity of the Fe(III) in the supernatant system was maintained with little loss in reactivity over at least 24 h. The capacity of SMPs to maintain high reactivity of AFO has important implications in a reactor where Fe(III) phases encounter alternating redox conditions due to sludge recirculation, creating a cycle of reductive dissolution, oxidation and precipitation. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Zhang, Hengzhong; Waychunas, Glenn A.; Banfield, Jillian F.
2015-07-29
Nucleation is a fundamental step in crystal growth. Of environmental and materials relevance are reactions that lead to nucleation of iron oxyhydroxides in aqueous solutions. These reactions are difficult to study experimentally due to their rapid kinetics. Here, we used classical molecular dynamics simulations to investigate nucleation of iron hydroxide/oxyhydroxide nanoparticles in aqueous solutions. Results show that in a solution containing ferric ions and hydroxyl groups, iron–hydroxyl molecular clusters form by merging ferric monomers, dimers, and other oligomers, driven by strong affinity of ferric ions to hydroxyls. When deprotonation reactions are not considered in the simulations, these clusters aggregate tomore » form small iron hydroxide nanocrystals with a six-membered ring-like layered structure allomeric to gibbsite. By comparison, in a solution containing iron chloride and sodium hydroxide, the presence of chlorine drives cluster assembly along a different direction to form long molecular chains (rather than rings) composed of Fe–O octahedra linked by edge sharing. Further, in chlorine-free solutions, when deprotonation reactions are considered, the simulations predict ultimate formation of amorphous iron oxyhydroxide nanoparticles with local atomic structure similar to that of ferrihydrite nanoparticles. Overall, our simulation results reveal that nucleation of iron oxyhydroxide nanoparticles proceeds via a cluster aggregation-based nonclassical pathway.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Pichler, T.; Veizer, J.; Hall, G.E.M.
The coral reef that circles Ambitle Island, Papua New Guinea, is exposed to the discharge of a hot, mineralized hydrothermal fluid. The hydrothermal fluids have a pH of {approximately}6 and are slightly reducing and rich in As. Seven individual vents discharge an estimated 1500 g of As per day into an area of approximately 50 x 100 m that has an average depth of 6 m. Despite the amount of As released into the bay, corals, clams, and fish do not show a response to the elevated values. The authors analyzed hydrothermal precipitates for their chemical and mineralogical composition inmore » order to determine As sinks. Two mechanisms efficiently control and buffer the As concentration: (1) dilution by seawater and (2) incorporation in and adsorption on Fe(III) oxyhydroxides that precipitate when the hydrothermal fluids mix with ambient seawater. Fe(III) oxyhydroxides contain up to 76,000 ppm As, by an order of magnitude the highest As values found in a natural marine environment. Following adsorption, As is successfully retained in the Fe(III) oxyhydroxide deposits because oxidizing conditions prevail and high As activity allows for the formation of discrete As minerals, such as claudetite, arsenic oxide, and scorodite.« less
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Sorption of arsenic to biogenic iron (oxyhydr)oxides produced in circumneutral environments
NASA Astrophysics Data System (ADS)
Sowers, Tyler D.; Harrington, James M.; Polizzotto, Matthew L.; Duckworth, Owen W.
2017-02-01
Arsenic (As) is a widespread and problematic pollutant that can be derived from natural or anthropogenic sources. Iron (oxyhydr)oxides readily sorb As and thus play critical roles in As cycling in terrestrial environments; however, little is known about the affinity and mechanism of As sorption by biogenic iron (oxyhydr)oxides formed in circumneutral environments. To investigate this, we conducted sorption isotherm and kinetics experiments to compare As(V) and As(III) sorption to synthetic 2-line ferrihydrite and iron biominerals harvested from the hyporheic zone of an uncontaminated creek. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify both As(V) and As(III), and X-ray absorption spectroscopy (XAS) was utilized to obtain As and Fe K-edge spectra for As(V) and As(III) sorbed to environmentally collected and laboratory produced Fe(III) minerals. All environmental Fe(III) biominerals were determined to be structurally similar to 2-line ferrihydrite. However, environmental Fe(III) biominerals have a surface area normalized affinity for As(V) and for As(III) that is greater than or equivalent to synthetic 2-line ferrihydrite. Whereas the extent of sorption was similar for As(III) on all minerals, As(V) sorption to environmental Fe(III) biominerals was approximately three times higher than what was observed for synthetic 2-line ferrihydrite. Structural modeling of EXAFS spectra revealed that the same surface complexation structure was formed by As(V) and by As(III) on environmental Fe(III) biominerals and ferrihydrite. These results suggest that, despite similarities in binding mechanisms, Fe(III) biominerals may be more reactive sorbents that synthetic surrogates often used to model environmental reactivity.
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Iron oxyhydroxide mineralization on microbial extracellular polysaccharides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.
2010-06-22
Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence ({mu}XRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolatedmore » from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.« less
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Influence of Humic Acid on Stability and Attachment of nTiO2 Particles to Sand at Different pH
NASA Astrophysics Data System (ADS)
Cheng, T.
2015-12-01
Stability of nano-scale or micro-scale titanium dioxide particles (nTiO2) and their attachment to sediment grains have important implications to the fate and transport of nTiO2 in subsurface environments. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand, with special attention to low HA concentration ranges that are relevant to groundwater conditions. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand were experimentally measured under a range of low HA concentrations at pH 5 and 9. Results showed that HA can either promote or hinder nTiO2 stability, depending on pH and HA concentration. We also found that HA can either enhance or reduce nTiO2 attachment to Fe oxyhydroxide coating at pH 5, depending on HA concentration. Results further showed that at pH 5, Fe oxyhydroxide coating reduced nTiO2 attachment to sand in the absence of HA but increased nTiO2 attachment in the presence of low concentration of HA. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was invoked to analyze particle-to-particle and particle-to-sand interactions in order to elucidate the roles of pH, HA, quartz, and Fe coating in nTiO2 stability and attachment. Overall, this study showed that changes in zeta potential of nTiO2 and Fe coating due to pH changes and/or HA adsorption are the key factors that influence stability and attachment of nTiO2.
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NASA Astrophysics Data System (ADS)
Simos, N.; Zhong, Z.; Dooryhee, E.; Ghose, S.; Gill, S.; Camino, F.; Şavklıyıldız, İ.; Akdoğan, E. K.
2017-06-01
The study revealed that loss of ductility in an amorphous Fe-alloy coating on a steel substrate composite structure was essentially prevented from occurring, following radiation with modest neutron doses of ∼2 × 1018 n/cm2. At the higher neutron dose of ∼2 × 1019, macroscopic stress-strain analysis showed that the amorphous Fe-alloy nanostructured coating, while still amorphous, experienced radiation-induced embrittlement, no longer offering protection against ductility loss in the coating-substrate composite structure. Neutron irradiation in a corrosive environment revealed exemplary oxidation/corrosion resistance of the amorphous Fe-alloy coating, which is attributed to the formation of the Fe2B phase in the coating. To establish the impact of elevated temperatures on the amorphous-to-crystalline transition in the amorphous Fe-alloy, electron microscopy was carried out which confirmed the radiation-induced suppression of crystallization in the amorphous Fe-alloy nanostructured coating.
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EAG Eminent Speaker: Cold war biogeochemistry: Microbes as architects for metal attenuation
NASA Astrophysics Data System (ADS)
Küsel, K.
2012-04-01
Legacy uranium mining in the area of Ronneburg, Germany, has resulted in extensive outflow of highly heavy metal contaminated ground and upcoming mine waters. Mine water flows along a grassland into a small creek and forms iron-rich precipitates yielding rust-colored terraces at the creek bank. These iron oxyhydroxides could have been formed by iron oxidizing bacteria (FeOB) or by chemical oxidation. Precipitates may serve as important biogeochemical interfaces, because heavy metals can adsorb or co-precipitate with Fe(II) or Fe(III) minerals. Thus, microbial Fe(II) oxidation but also the reductive dissolution of iron oxides can be important processes affecting the stability of metal contaminants. Here we present a study on the potential for iron cycling processes and on indigenous bacterial communities in this acidic creek. Oxic and anoxic in vitro sediment incubations revealed iron oxidation and reduction rates of same magnitude, indicating active iron cycling regardless of pH. XRD and TEM comparing the suspended particle load of water samples with fresh creek sediment showed that amorphous particles likely formed first, then aged to become more crystalline iron oxyhydroxides, such as akaganeite and goethite. During this aging process some of the initially smooth, 50-300 nm spherical particles may have formed nano-sized needles, which could potentially provide high reactive surface area for chemical and biological reactions. Surprisingly, total and dissolved metal concentrations in creek water and sediment revealed that elements such as Mn, Si, Ni, or Zn stayed mostly in solution. Only some metals such as Cu, Cr, and U seemed to be particle-associated in the water, likely co-precipitated with or adsorbed onto freshly-precipitating minerals. Pelagic and particle-associated organisms from water as well as fresh sediments were used for 16S rRNA gene cloning and sequencing and showed that members of the Proteobacteria (mainly Betaproteobacteria and Deltaproteobacteria) dominated bacterial communities. The relative fraction of FeOB-related clones was especially high in upcoming underground water and sediment of the adjacent creek site. Up to 80% of clones in sediment microbial 16S rRNA gene clone libraries had ≥97% sequence similarity to reported FeOM or FeRM, demonstrating a strong link to function, even on RNA level. Three novel moderately acidophilic FeOM strains, Thiomonas sp. FB-Cd and FB-6 and Bordetella sp. FB-8, were isolated from pH 6.3 sediment. FB-6 is likely involved in in situ iron oxidation as it has high similarity to a RNA-derived clone from this sediment. Our results demonstrated active microbial iron cycling in heavy metal contaminated creeks, which have important implications for understanding natural attenuation.
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Dynamics of copper and zinc sedimentation in a lagooning system receiving landfill leachate.
Guigue, Julien; Mathieu, Olivier; Lévêque, Jean; Denimal, Sophie; Steinmann, Marc; Milloux, Marie-Jeanne; Grisey, Hervé
2013-11-01
This study characterises the sediment dredged from a lagooning system composed of a settling pond and three lagoons that receive leachates from a municipal solid waste (MSW) landfill in France. Organic carbon, carbonate, iron oxyhydroxides, copper (Cu) and zinc (Zn) concentrations were measured in the sediment collected from upstream to downstream in the lagooning system. In order to complete our investigation of sedimentation mechanisms, leachates were sampled in both dry (spring) and wet (winter) seasonal conditions. Precipitation of calcite and amorphous Fe-oxyhydroxides and sedimentation of organic matter occurred in the settling pond. Since different distributions of Zn and Cu concentrations are measured in sediment samples collected downstream in the lagooning system, it is suggested that these elements were not distributed in a similar way in the leachate fractions during the first stage of treatment in the settling pond, so that their sedimentation dynamics in the lagooning system differ. In the lagoons, it was found that organic carbon plays a major role in Cu and Zn mobility and trapping. The presence of macrophytes along the edges provided an input of organic matter that enhanced Cu and Zn scavenging. This edge effect resulted in a two-fold increase in Cu and Zn concentrations in the sediment deposited near the banks of the lagoons, thus confirming the importance of vegetation for the retention of Cu and Zn in lagooning systems. Copyright © 2013 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, D.; Kaplan, D.
2012-02-29
The Savannah River Site (SRS) has conducted performance assessment (PA) calculations to determine the risk associated with closing liquid waste tanks. The PA estimates the risk associated with a number of scenarios, making various assumptions. Throughout all of these scenarios, it is assumed that the carbon-steel tank liners holding the liquid waste do not sorb the radionuclides. Tank liners have been shown to form corrosion products, such as Fe-oxyhydroxides (Wiersma and Subramanian 2002). Many corrosion products, including Fe-oxyhydroxides, at the high pH values of tank effluent, take on a very strong negative charge. Given that many radionuclides may have netmore » positive charges, either as free ions or complexed species, it is expected that many radionuclides will sorb to corrosion products associated with tank liners. The objective of this report was to conduct a literature review to investigate whether Pu, U, Np, Am and Tc would sorb to corrosion products on tank liners after they were filled with reducing grout (cementitious material containing slag to promote reducing conditions). The approach was to evaluate radionuclides sorption literature with iron oxyhydroxide phases, such as hematite ({alpha}-Fe{sub 2}O{sub 3}), magnetite (Fe{sub 3}O{sub 4}), goethite ({alpha}-FeOOH) and ferrihydrite (Fe{sub 2}O{sub 3} {center_dot} 0.5H{sub 2}O). The primary interest was the sorption behavior under tank closure conditions where the tanks will be filled with reducing cementitious materials. Because there were no laboratory studies conducted using site specific experimental conditions, (e.g., high pH and HLW tank aqueous and solid phase chemical conditions), it was necessary to extend the literature review to lower pH studies and noncementitious conditions. Consequently, this report relied on existing lower pH trends, existing geochemical modeling, and experimental spectroscopic evidence conducted at lower pH levels. The scope did not include evaluating the appropriateness of K{sub d} values for the Fe-oxyhydroxides, but instead to evaluate whether it is a conservative assumption to exclude this sorption process of radionuclides onto tank liner corrosion products in the PA model. This may identify another source for PA conservatism since the modeling did not consider any sorption by the tank liner.« less
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Han, Young Soo; Jeong, Hoon Young; Hyun, Sung Pil; Hayes, Kim F; Chon, Chul Min
2018-05-01
During X-ray absorption spectroscopy (XAS) measurements of arsenic (As), beam-induced redox transformation is often observed. In this study, the As species immobilized by poorly crystallized mackinawite (FeS) was assessed for the susceptibility to beam-induced redox reactions as a function of sample properties including the redox state of FeS and the solid-phase As speciation. The beam-induced oxidation of reduced As species was found to be mediated by the atmospheric O 2 and the oxidation products of FeS [e.g. Fe(III) (oxyhydr)oxides and intermediate sulfurs]. Regardless of the redox state of FeS, both arsenic sulfide and surface-complexed As(III) readily underwent the photo-oxidation upon exposure to the atmospheric O 2 during XAS measurements. With strict O 2 exclusion, however, both As(0) and arsenic sulfide were less prone to the photo-oxidation by Fe(III) (oxyhydr)oxides than NaAsO 2 and/or surface-complexed As(III). In case of unaerated As(V)-reacted FeS samples, surface-complexed As(V) was photocatalytically reduced during XAS measurements, but arsenic sulfide did not undergo the photo-reduction.
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Fate of Cd during microbial Fe(III) mineral reduction by a novel and Cd-tolerant Geobacter species.
Muehe, E Marie; Obst, Martin; Hitchcock, Adam; Tyliszczak, Tolek; Behrens, Sebastian; Schröder, Christian; Byrne, James M; Michel, F Marc; Krämer, Ute; Kappler, Andreas
2013-12-17
Fe(III) (oxyhydr)oxides affect the mobility of contaminants in the environment by providing reactive surfaces for sorption. This includes the toxic metal cadmium (Cd), which prevails in agricultural soils and is taken up by crops. Fe(III)-reducing bacteria can mobilize such contaminants by Fe(III) mineral dissolution or immobilize them by sorption to or coprecipitation with secondary Fe minerals. To date, not much is known about the fate of Fe(III) mineral-associated Cd during microbial Fe(III) reduction. Here, we describe the isolation of a new Geobacter sp. strain Cd1 from a Cd-contaminated field site, where the strain accounts for 10(4) cells g(-1) dry soil. Strain Cd1 reduces the poorly crystalline Fe(III) oxyhydroxide ferrihydrite in the presence of at least up to 112 mg Cd L(-1). During initial microbial reduction of Cd-loaded ferrihydrite, sorbed Cd was mobilized. However, during continuous microbial Fe(III) reduction, Cd was immobilized by sorption to and/or coprecipitation within newly formed secondary minerals that contained Ca, Fe, and carbonate, implying the formation of an otavite-siderite-calcite (CdCO3-FeCO3-CaCO3) mixed mineral phase. Our data shows that microbially mediated turnover of Fe minerals affects the mobility of Cd in soils, potentially altering the dynamics of Cd uptake into food or phyto-remediating plants.
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Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike; Bernsmeier, Denis; Dresp, Sören; Gliech, Manuel; Jusys, Zenonas; Chernev, Petko; Kraehnert, Ralph; Dau, Holger; Strasser, Peter
2017-02-08
Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O 2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni +3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni +3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.
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Simos, N.; Zhong, Z.; Dooryhee, E.; ...
2017-03-23
Here, this study revealed that loss of ductility in an amorphous Fe-alloy coating on a steel substrate composite structure was essentially prevented from occurring, following radiation with modest neutron doses of ~2 x 10 18 n/cm 2. At the higher neutron dose of ~2 x 10 19, macroscopic stress-strain analysis showed that the amorphous Fe-alloy nanostructured coating, while still amorphous, experienced radiation-induced embrittlement, no longer offering protection against ductility loss in the coating-substrate composite structure. Neutron irradiation in a corrosive environment revealed exemplary oxidation/corrosion resistance of the amorphous Fe-alloy coating, which is attributed to the formation of the Fe 2Bmore » phase in the coating. To establish the impact of elevated temperatures on the amorphous-to-crystalline transition in the amorphous Fe-alloy, electron microscopy was carried out which confirmed the radiation-induced suppression of crystallization in the amorphous Fe-alloy nanostructured coating.« less
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NASA Astrophysics Data System (ADS)
Vazquez, A.; Hernández, S.; Rasmussen, C.; Chorover, J.
2010-12-01
Al and Fe oxy-hydroxide minerals have been implicated in dissolved organic matter (DOM) stabilization. DOM solutions from a Pinus ponderosa forest floor (PPDOM) were used to irrigate polypropylene columns, 3.2 cm long by 0.9 cm diameter (total volume 2.0 cm3), that were packed with quartz sand (QS), gibbsite-quartz sand (Al-QS), and goethite-quartz sand (Fe-QS) mixtures. To investigate the mobilization and fractionation of DOM during reactive transport, effluent solutions were characterized by UV-Vis absorbance and excitation-emission matrix (EEM) fluorescence spectroscopies. Magnitude of PPDOM sorption followed the trend Al-QS > Fe-QS > QS during the initial transport. Effluent pH values suggest that ligand exchange is a primary mechanism for PPDOM sorption onto oxy-hydroxide minerals. Low molar absorptivity values were observed in effluent solutions of early pore volumes, indicating preferential mobilization of compounds with low aromatic character. Compounds traditionally characterized by EEM spectroscopy as being more highly humified were favorably absorbed onto the gibbsite and goethite surfaces. Humification index values (HIX) were also correlated with DOM aromaticity. HIX results suggest that the presence of low mass fractions of oxy-hydroxide minerals affect the preferential uptake of high molar mass constituents of PPDOM during reactive transport.
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Geochemical evolution of solutions derived from experimental weathering of sulfide-bearing rocks
Munk, L.; Faure, G.; Koski, R.
2006-01-01
The chemical composition of natural waters is affected by the weathering of geologic materials at or near the surface of the Earth. Laboratory weathering experiments of whole-rock sulfide rocks from the Shoe-Basin Mine (SBM) and the Pennsylvania Mine (PM) from the Peru Creek Basin, Summit County, Colorado, indicate that the mineral composition of the sulfide rocks, changes in pH, the duration of the experiment, and the formation of sorbents such as Fe and Al oxyhydroxides affect the chemical composition of the resulting solution. Carbonate minerals in the rock from SBM provide buffering capacity to the solution, contribute to increases in the pH and enhance the formation of Fe and Al oxyhydroxides, which sorb cations from solution. The final solution pH obtained in the experiments was similar to those measured in the field (i.e., 2.8 for PM and 5.0 for SBM). At PM, acidic, metal-rich mine effluent is discharged into Peru Creek where it mixes with stream water. As a result, the pH of the effluent increases causing Fe and Al oxyhydroxide and schwertmannite to precipitate. The resulting solids sorb metal cations from the water thereby improving the quality of the water in Peru Creek. ?? 2006.
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The secret behind the success of doping nickel oxyhydroxide with iron.
Fidelsky, Vicky; Toroker, Maytal Caspary
2017-03-15
Discovering better catalysts for water splitting is the holy grail of the renewable energy field. One of the most successful water oxidation catalysts is nickel oxyhydroxide (NiOOH), which is chemically active only as a result of doping with Fe. In order to shed light on how Fe improves efficiency, we perform Density Functional Theory +U (DFT+U) calculations of water oxidation reaction intermediates of Fe substitutional doped NiOOH. The results are analyzed while considering the presence of vacancies that we use as probes to test the effect of adding charge to the surface. We find that the smaller electronegativity of the Fe dopant relative to Ni allows the dopant to have several possible oxidation states with less energy penalty. As a result, the presence of vacancies which alters local oxidation states does not affect the low overpotential of Fe-doped NiOOH. We conclude that the secret to the success of doping NiOOH with iron is the ability of iron to easily change oxidation states, which is critical during the chemical reaction of water oxidation.
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Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Doyle, Andrew D.; Bajdich, Michal; Vojvodic, Aleksandra
The nature of the electrochemical water splitting activity of layered pure and Fe-doped NiOOH is investigated using density functional theory calculations. We find similar thermodynamics for the oxygen evolution reaction (OER) intermediates between the layers of oxyhydroxides, that is, in the bulk of the materials as on the (001) surface. The effect of interlayer spacing on adsorption energy is affected by both the crystal structure and the level of hydrogenation of the active sites. For the Fe-doped NiOOH, we observe general weakening of binding between the different OER intermediates and the catalyst material. The calculated OER activity depends both onmore » doping and interlayer spacing, and our results are generally congruent with available experimental data. In conclusion, these results suggest that such interlayer “bulk” sites may contribute to measured OER activity for both the pure and Fe-doped NiOOH catalysts.« less
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Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides
Doyle, Andrew D.; Bajdich, Michal; Vojvodic, Aleksandra
2017-04-07
The nature of the electrochemical water splitting activity of layered pure and Fe-doped NiOOH is investigated using density functional theory calculations. We find similar thermodynamics for the oxygen evolution reaction (OER) intermediates between the layers of oxyhydroxides, that is, in the bulk of the materials as on the (001) surface. The effect of interlayer spacing on adsorption energy is affected by both the crystal structure and the level of hydrogenation of the active sites. For the Fe-doped NiOOH, we observe general weakening of binding between the different OER intermediates and the catalyst material. The calculated OER activity depends both onmore » doping and interlayer spacing, and our results are generally congruent with available experimental data. In conclusion, these results suggest that such interlayer “bulk” sites may contribute to measured OER activity for both the pure and Fe-doped NiOOH catalysts.« less
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Biomineralogy and Morphology of the Marine Iron-oxidizing Bacterium Mariprofundus ferrooxydans
NASA Astrophysics Data System (ADS)
Chan, C. S.; Emerson, D.; Edwards, K. J.
2006-12-01
Mariprofundus ferrooxydans strain PV-1 is a lithoautotrophic iron-oxidizing proteobacterium isolated from the Loihi Seamount in Hawaii. As cells grow, they form filaments upon which iron minerals are deposited. Based on similarities in morphology, these structures appear to accumulate and form the bulk of iron mats at Loihi. Furthermore, Mariprofundus has been observed in a number of other seafloor mat samples (e.g. by microscopy and 16S rRNA gene sequencing of East Pacific Rise samples, C. M. Santelli unpublished data), suggesting that the occurrence of Mariprofundus is widespread. To learn about the effect of Mariprofundus on iron cycling, we are studying the processes by which it oxidizes iron and influences iron mineral formation. We are conducting studies on the spatial relationships between the cells, stalks, and minerals using scanning and transmission electron microscopy (SEM and TEM). Identification and imaging of stalk-bound, nanometer-sized iron oxyhydroxide minerals is being performed by high-resolution transmission electron microscopy (HRTEM). We have developed sample preparation methods to preserve in vivo spatial relationships, involving direct colonization of sample holders in cultures and in the environment. Method development has been performed on stalk-forming, iron-oxidizing Gallionella ferruginea cultures and terrestrial iron mats. Gallionella is morphologically and physiologically very similar to Mariprofundus, although 16S rRNA gene phylogeny shows that they are not closely related. Comparison of the terrestrial and marine iron-oxidizing bacteria (FeOB) gives us insight into adaptations that are particular to marine iron-oxidizers and those that are common to all FeOB. Light and fluorescence microscopy of Mariprofundus cultures has shown that a single bean-shaped cell lies at the end of each filament. SEM and TEM results have revealed that the filament is ribbon-like, sometimes twisted as with the classic Gallionella stalk, but sometimes not. Filaments formed in culture have been measured at 0.5 and 1.7 microns in width and as long as 70 microns. They are composed of a varying number of parallel subfilaments, each approximately 70 nm in width. HRTEM observations show that lightly-mineralized filaments are covered in nanometer-size, poorly crystalline, and possibly amorphous iron oxyhydroxides, which likely represent an early stage in filament mineralization. Highly-mineralized filaments are coated in lepidocrocite and akaganeite (both iron oxyhydroxides), in random crystallographic orientations. The more crystalline minerals probably result from recrystallization of the initially-deposited FeOOH and continued precipitation on the filament. We will revisit Loihi in October to collect fresh, undisturbed samples for electron microscopy, in order to compare cultured and natural samples. This work is being performed in conjunction with genomic and protein analyses aimed at identifying the genes involved in iron oxidation.
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Morphology and phase control of iron oxide polymorph nanoparticles
NASA Astrophysics Data System (ADS)
Cui, Hongtao; Wang, Li; Shi, Min; Li, Yanhong
2017-04-01
In this work, lepidocrocite (γ-FeOOH) nanobundles were prepared by a facile NH4F assisted epoxide precipitation route. The reactions between epoxide and [Fe(H2O)6]2+ promoted the hydrolysis and condensation of [Fe(H2O)6]2+, resulting in the formation of iron oxyhydroxide. After calcination of γ-FeOOH nanobundles at 400 °C, the produced α-Fe2O3 still kept the bundle morphology. Due to the unique chemistry of epoxide, the morphology and phase of iron oxide polymorph nanoparticles (goethite, akaganeite, lepidocrocite, magnetite) were well-controlled through controlling reaction conditions such as Fe2+ concentration, NH4F additive and reaction temperature. It is particularly interesting that NH4F working as phase controlling agent is able to control the phase development of iron oxyhydroxides. This phase control effect of NH4F is attributed to the promoted reaction rate of epoxide originating from the higher electronegativity of fluoride ions than chloride ions. Based on the results in this work and our other preliminary works, it is considered that this route can be used as a general strategy for controlling the morphology and phase of transition element compounds.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
David R. Veblen; Chen Zhu; Lee Krumholz
The effectiveness and feasibility of bioremediation at the field scale cannot be fully assessed until the mechanisms of immobilization and U speciation in the solid matrix are resolved. However, characterization of the immobilized U and its valence states is extremely difficult, because microbially mediated mineral precipitates are generally nanometer (nm)-sized, poorly crystalline, or amorphous. We are developing combined field emission gun--scanning electron microscopy (FEG-SEM, at Indiana University) and FEG transmission electron microscopy (TEM, at Hopkins) to detect and isolate uranium containing phases; (1) method developments for TEM sample preparations and parallel electron energy loss spectroscopy (EELS) determination of uranium valence;more » and (2) to determine the speciation, fate, reactivity, valence states of immobilized uranium, using the state-of-the-art 300-kV, FEG-TEM. We have obtained preliminary results on contaminated sediments from Area 3 at the Oak Ridge Field Research Center (FRC). TEM results show that the sediments contain numerous minerals, including quartz, mica/clay (muscovite and/or illite), rutile, ilmenite, zircon, and an Al-Sr-Ce-Ca phosphate mineral, none of which contain uranium above the EDS detection limit. Substantial U (up to {approx}2 wt.%) is, however, clearly associated with two materials: (1) the Fe oxyhydroxide and (2) clots of a chemically complex material that is likely a mixture of several nm-scale phases. The Fe oxyhydroxide was identified as goethite from its polycrystalline SAED pattern and EDS analysis showing it to be very Fe-rich; the aggregate also displays one of several morphologies that are common for goethite. U is strongly sorbed to goethite in the FRC sediment, and the ubiquitous association with phosphorous suggests that complexes containing both U and P may play an important role in that sorption. Results from bulk analysis and SEM had previously demonstrated the association of U with Fe and thus suggested that U may be sorbed by Fe oxide or oxyhydroxide (Dr. Roh, image presented by David Watson). However, rigorous identification of the host minerals for U requires TEM results such as these involving imaging, electron diffraction, and spectroscopic analysis. An even higher concentration of U occurs in the chemically complex material noted above. These ''clots'' are high in Fe but also contain C, O, Mg, Al, Si, P, S, Cl, K, Ca, Mn, and U. This chemical complexity strongly suggests that they consist of aggregates of carbonate, silicate, phosphate, and sulfate phases, and TEM images also suggest that they may be intergrowths of numerous exceedingly small nanoparticles. EELS and EFTEM studies should be able to resolve these various components and identify precisely where the uranium is in these complex materials. From the results, it is clear that the FEG-SEM and FEG-TEM can readily detect uranium in the FRC samples. The FEG-SEM allows a wide field of view of the samples and can detect U-rich aggregates as small as 20-30 nm. The FEG-TEM can then focus on these aggregates and use SAED, EDS, EFTEM, and PEELS techniques to determine the valence states, structures, and compositional data for these aggregates. This research will provide a crucial component for a complete understanding of the efficacy of uranium bioremediation.« less
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Koschinsky, A.; Hein, J.R.
2003-01-01
Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.
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Paktunc, Dogan; Foster, Andrea; Laflamme, Gilles
2003-05-15
Ketza River mine tailings deposited underwater and those exposed near the tailings impoundment contain approximately 4 wt % As. Column-leaching tests indicated the potential for high As releases from the tailings. The tailings are composed dominantly of iron oxyhydroxides, quartz, calcite, dolomite, muscovite, ferric arsenates, and calcium-iron arsenates. Arsenopyrite and pyrite are trace constituents. Chemical compositions of iron oxyhydroxide and arsenate minerals are highly variable. The XANES spectra indicate that arsenic occurs as As(V) in tailings, but air-drying prior to analysis may have oxidized lower-valent As. The EXAFS spectra indicate As-Fe distances of 3.35-3.36 A for the exposed tailings and 3.33-3.35 A for the saturated tailings with coordination numbers of 0.96-1.11 and 0.46-0.64, respectively. The As-Ca interatomic distances ranging from 4.15 to 4.18 A and the coordination numbers of 4.12-4.58 confirm the presence of calcium-iron arsenates in the tailings. These results suggest that ferric arsenates and inner-sphere corner sharing or bidentate-binuclear attachment of arsenate tetrahedra onto iron hydroxide octahedra are the dominant form of As in the tailings. EXAFS spectra indicate that the exposed tailings are richer in arsenate minerals whereas the saturated tailings are dominated by the iron oxyhydroxides, which could help explain the greater release of As from the exposed tailings during leaching tests. It is postulated that the dissolution of ferric arsenates during flow-through experiments caused the high As releases from both types of tailings. Arsenic tied to iron oxyhydroxides as adsorbed species are considered stable; however, iron oxyhydroxides having low Fe/As molar ratios may not be as stable. Continued As releases from the tailings are likely due to dissolution of both ferric and calcium-iron arsenates and desorption of As from high-As bearing iron oxyhydroxides during aging.
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Paktunc, D.; Foster, A.; Laflamme, G.
2003-01-01
Ketza River mine tailings deposited underwater and those exposed near the tailings impoundment contain approximately 4 wt % As. Column-leaching tests indicated the potential for high As releases from the tailings. The tailings are composed dominantly of iron oxyhydroxides, quartz, calcite, dolomite, muscovite, ferric arsenates, and calcium-iron arsenates. Arsenopyrite and pyrite are trace constituents. Chemical compositions of iron oxyhydroxide and arsenate minerals are highly variable. The XANES spectra indicate that arsenic occurs as As(V) in tailings, but air-drying prior to analysis may have oxidized lower-valent As. The EXAFS spectra indicate As-Fe distances of 3.35-3.36 A?? for the exposed tailings and 3.33-3.35 A?? for the saturated tailings with coordination numbers of 0.96-1.11 and 0.46-0.64, respectively. The As-Ca interatomic distances ranging from 4.15 to 4.18 A?? and the coordination numbers of 4.12-4.58 confirm the presence of calcium-iron arsenates in the tailings. These results suggest that ferric arsenates and inner-sphere corner sharing or bidentatebinuclear attachment of arsenate tetrahedra onto iron hydroxide octahedra are the dominant form of As in the tailings. EXAFS spectra indicate that the exposed tailings are richer in arsenate minerals whereas the saturated tailings are dominated by the iron oxyhydroxides, which could help explain the greater release of As from the exposed tailings during leaching tests. It is postulated that the dissolution of ferric arsenates during flow-through experiments caused the high As releases from both types of tailings. Arsenic tied to iron oxyhydroxides as adsorbed species are considered stable; however, iron oxyhydroxides having low Fe/As molar ratios may not be as stable. Continued As releases from the tailings are likely due to dissolution of both ferric and calcium-iron arsenates and desorption of As from high-As bearing iron oxyhydroxides during aging.
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Yu, K. Y.; Fan, Z.; Chen, Y.; ...
2014-08-26
Enhanced irradiation tolerance in crystalline multilayers has received significant attention lately. However, little is known on the irradiation response of crystal/amorphous nanolayers. We report on in situ Kr ion irradiation studies of a bulk Fe 96Zr 4 nanocomposite alloy. Irradiation resulted in amorphization of Fe 2Zr and formed crystal/amorphous nanolayers. α-Fe layers exhibited drastically lower defect density and size than those in large α-Fe grains. In situ video revealed that mobile dislocation loops in α-Fe layers were confined by the crystal/amorphous interfaces and kept migrating to annihilate other defects. This study provides new insights on the design of irradiation-tolerant crystal/amorphousmore » nanocomposites.« less
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Civeira, Matheus S; Pinheiro, Rafael N; Gredilla, Ainara; de Vallejuelo, Silvia Fdez Ortiz; Oliveira, Marcos L S; Ramos, Claudete G; Taffarel, Silvio R; Kautzmann, Rubens M; Madariaga, Juan Manuel; Silva, Luis F O
2016-02-15
Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health. Copyright © 2015 Elsevier B.V. All rights reserved.
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Toughening Fe-based Amorphous Coatings by Reinforcement of Amorphous Carbon.
Wang, Wei; Zhang, Cheng; Zhang, Zhi-Wei; Li, Yi-Cheng; Yasir, Muhammad; Wang, Hai-Tao; Liu, Lin
2017-06-22
Toughening of Fe-based amorphous coatings meanwhile maintaining a good corrosion resistance remains challenging. This work reports a novel approach to improve the toughness of a FeCrMoCBY amorphous coating through in-situ formation of amorphous carbon reinforcement without reducing the corrosion resistance. The Fe-based composite coating was prepared by high velocity oxy-fuel (HVOF) thermal spraying using a pre-mixed Fe-based amorphous/nylon-11 polymer feedstock powders. The nylon-11 powders were in-situ carbonized to amorphous carbon phase during thermal spraying process, which homogeneously distributed in the amorphous matrix leading to significant enhancement of toughness of the coating. The mechanical properties, including hardness, impact resistance, bending and fatigue strength, were extensively studied by using a series of mechanical testing techniques. The results revealed that the composite coating reinforced by amorphous carbon phase exhibited enhanced impact resistance and nearly twice-higher fatigue strength than that of the monolithic amorphous coating. The enhancement of impact toughness and fatigue properties is owed to the dumping effect of the soft amorphous carbon phase, which alleviated stress concentration and decreased crack propagation driving force.
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Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; ...
2017-05-19
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here in this work, we have measured themore » redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). Lastly, we present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.« less
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NASA Astrophysics Data System (ADS)
Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.
2017-08-01
Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.
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Kuippers, Gina; Boothman, Christopher; Bagshaw, Heath; Ward, Michael; Beard, Rebecca; Bryan, Nicholas; Lloyd, Jonathan R
2018-06-08
Intermediate level radioactive waste (ILW) generally contains a heterogeneous range of organic and inorganic materials, of which some are encapsulated in cement. Of particular concern are cellulosic waste items, which will chemically degrade under the conditions predicted during waste disposal, forming significant quantities of isosaccharinic acid (ISA), a strongly chelating ligand. ISA therefore has the potential to increase the mobility of a wide range of radionuclides via complex formation, including Ni-63 and Ni-59. Although ISA is known to be metabolized by anaerobic microorganisms, the biodegradation of metal-ISA complexes remains unexplored. This study investigates the fate of a Ni-ISA complex in Fe(III)-reducing enrichment cultures at neutral pH, representative of a microbial community in the subsurface. After initial sorption of Ni onto Fe(III)oxyhydroxides, microbial ISA biodegradation resulted in >90% removal of the remaining Ni from solution when present at 0.1 mM, whereas higher concentrations of Ni proved toxic. The microbial consortium associated with ISA degradation was dominated by close relatives to Clostridia and Geobacter species. Nickel was preferentially immobilized with trace amounts of biogenic amorphous iron sulfides. This study highlights the potential for microbial activity to help remove chelating agents and radionuclides from the groundwater in the subsurface geosphere surrounding a geodisposal facility.
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NASA Astrophysics Data System (ADS)
McCollom, T. M.; Hynek, B. M.
2012-12-01
The Mars Exploration Rover (MER) Opportunity has extensively characterized sulfate-rich, hematite-bearing bedrock exposed at Meridiani Planum, Mars. Based on various measurements, the mineral composition of the bedrocks has been interpreted to include: amorphous silica/glass/phyllosilicates, Mg-, Ca-, and Fe-bearing sulfates including jarosite, minor amounts of igneous phases including plagioclase, pyroxene, olivine, and magnetite, and hematite [1,2]. Chemically, the bedrocks closely resemble the composition of pristine martian basalt with addition of S and O, and minor variations of Mg and Cl with depth [3,4]. Based on these and other observations, the MER team has proposed that the bedrocks represent chemically altered siliciclastic sediments combined with sulfate salts formed by evaporation of sulfate-bearing fluids, modified by transport and multiple stages of infiltrating groundwater [3,5]. Several alternative scenarios have been proposed for the origin of the rocks including large impacts [6], evaporating glacial deposits [7], acid-fog alteration [8], and hydrothermal acid-sulfate alteration of basalt [4]. In order to further evaluate the potential contribution of hydrothermal proceeses to the deposits, we performed numerical geochemical models of acid-sulfate alteration of martian basalt based on constraints provided by recent laboratory experiments. Experimental studies of alteration of basalt conducted in our lab [9] indicate that the initial stages of acid-sulfate alteration of pyroclastic basalt are characterized by rapid decomposition of igneous crystalline phases including plagioclase, pyroxene, and olivine, while the glass (and igneous phases protected within the glass) remain unreactive. Elements released by dissolving minerals are precipitated primarily as amorphous silica and Ca-, Al-, Fe- and Mg-bearing sulfates, while precipitation of phyllosilicates and Fe-oxides/oxyhydroxides (FeOx) is kinetically inhibited. Based on these constraints, models of acid-sulfate alteration of martian pyroclastic basalt predict that the early stages of alteration will produce amorphous silica, anhydrite (or gypsum at lower temperature), Fe-bearing natroalunite, and kieserite as predominant secondary phases, along with relict glass and silicates protected within the glass. Hematite may form with continued heating through partial decomposition of Fe-bearing natroalunite [9], and some of the glass phase may partially devitrify to form minor phyllosilicates such as nontronite and nanophase Fe oxides. The resulting rock would have a chemical and mineralogical composition closely resembling that observed at Meridiani Planum. We conclude that hydrothermal acid-sulfate alteration of pyroclastic basalt provides the most parsimonious explanation for the composition of the sulfate deposits. References: [1] Glotch et al., JGR (2006). [2] Klingelhöfer et al. Science (2004). [3] McLennan et al., EPSL (2005). [4] McCollom & Hynek, Nature (2005). [5] Squyres et al. Science (2006). [6] Knauth et al. Nature (2005). [7] Niles & Michalski, Nat. Geosci. (2009). [8] Berger et al. Am. Mineral. (2009). [9] McCollom et al. JGR-Planets (submitted ms.)
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Effects of the addition of Co, Ni or Cr on the decolorization properties of Fe-Si-B amorphous alloys
NASA Astrophysics Data System (ADS)
Zhang, Changqin; Zhu, Zhengwang; Zhang, Haifeng
2017-11-01
Fe-based amorphous alloys show great potential in degrading azo dyes and other organic pollutants, and are widely investigated as a kind of environmental-friendly materials for wastewater remediation. In this paper, the effects of Co, Ni or Cr addition on the decolorization properties of Fe-Si-B amorphous alloys were studied, and the mechanism of their different effects was analyzed. Co addition could lower the activation energy of Fe-Si-B amorphous alloys in decolorizing azo dyes, and had no weakening effect on the decolorization capability of Fe-Si-B amorphous alloys. Ni addition led to partial crystallization of Fe-Si-B amorphous alloys, and the decolorization mechanism at low temperatures changed from chemical degradation to physical adsorption. Cr addition could enhance the corrosion resistance of Fe-Si-B amorphous alloys, but the amorphous alloys completely lost the decolorization capability no matter at lower or higher temperatures. The results of X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) indicated that the addition of Co, Ni or Cr could generate different surface structures that had significant influences on the decolorization process. Our work demonstrated that the effiecient decolorization of azo dyes by Fe-based alloys could be realized only when amorphous nature and incompact surface structure were simultaneously achieved for the alloys.
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Authigenic vivianite in Potomac River sediments: control by ferric oxy-hydroxides.
Hearn, P.P.; Parkhurst, D.L.; Callender, E.
1983-01-01
Sand-size aggregates of vivianite crystals occur in the uppermost sediments of the Potomac River estuary immediately downstream from the outfall of a sewage treatment plant at the southernmost boundary of the District of Columbia, USA. They are most abundant in a small area of coarse sand (dredge spoil) which contrasts with the adjacent, much finer sediments. The sewage outfall supplies both reducing conditions and abundant phosphate. Analyses and calculations indicate that the pore waters in all the adjacent sediments are supersaturated with respect to vivianite. Its concentration in the coarse sand is attributed to the absence there of amorphous ferric oxyhydroxides, which are present in the finer sediments and preferentially absorb the phosphate ion. -H.R.B.
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Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.
2008-01-01
Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.
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NASA Astrophysics Data System (ADS)
Surour, Adel A.
2015-01-01
In the Jabal Samran area (western Saudi Arabia), secondary copper mineralization in a NE-trending shear zone in which the arc metavolcanic host rocks (dacite-rhyodacite) show conjugate fractures and extensive hydrothermal alteration and bleaching. The zones contain frequent Fe-Mn(III) oxyhydroxides (FeOH-MnOH) that resulted from oxidation of pyrite and Mn-bearing silicates. In the bleached part, the groundmass is represented by Fe-bearing interstratified illite-smectite with up to 4.02 wt% FeOt. FeOH-MnOH are pre-weathering phases formed by hydrothermal alteration in a submarine environment prior to uplifting. Five varieties of FeOH are distinguished, four of them are exclusively hydrothermal with ∼20 wt% H2O whereas the fifth contains ∼31-33 wt% H2O and might represent reworking of earlier hydrothermal FeOH phases by weathering. FeOH fills thin fractures in the form of veinlets and crenulated laminae or as a pseudomorph for pyrite, goethite and finally ferrihydrite, and this oxyhydroxide is characterized by positive correlation of Fe2O3 with SiO2 and Al2O3. On the other hand, MOH shows positive correlation between MnO2 and Al2O3 whereas it is negative between Fe2O3 and SiO2. Paratacamite is the most common secondary copper mineral that fills fractures and post-dates FeOH and MnOH. It is believed that Cl- in the structure of paratacamite represents inherited marine storage rather than from surfacial evaporates or meteoric water. The mineralogy of slags suggests a complicated mineral assemblage that includes native Cu prills, synthetic spinifixed Mn-rich amphiboles with 16.73 wt% MnO, brown glass and Ca-Mn-Fe phase close to the olivine structure. EMPA indicate that the some Cu prills have either grey discontinuous boarder zone of S-rich Mn-Cu alloy (with up to 21.95 wt% S and 19.45 wt% Mn) or grey Cu-Mn-Fe alloy (with up to 15.9 wt% Cu, 39. 12 wt% Mn and 61.64 wt% Fe). Mn in the Cu prills is expelled inward as Cu-Mn-Fe alloy inclusions whereas S is expelled outward as S-rich Mn-Cu alloy crust. Remains in the Samran smelter sites suggest the use of charcoal as a source of energy, quartzite as a flux and an air-cooling technique was used.
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Minor-Cu doped soft magnetic Fe-based FeCoBCSiCu amorphous alloys with high saturation magnetization
NASA Astrophysics Data System (ADS)
Li, Yanhui; Wang, Zhenmin; Zhang, Wei
2018-05-01
The effects of Cu alloying on the amorphous-forming ability (AFA) and magnetic properties of the P-free Fe81Co5B11C2Si1 amorphous alloy were investigated. Addition of ≤ 1.0 at.% Cu enhances the AFA of the base alloy without significant deterioration of the soft magnetic properties. The Fe80.5Co5B11C2Si1Cu0.5 alloy with the largest critical thickness for amorphous formation of ˜35 μm possesses a high saturation magnetization (Bs) of ˜1.78 T, low coercivity of ˜14.6 A/m, and good bending ductility upon annealing in a wide temperature range of 513-553 K with maintaining the amorphous state. The fabrication of the new high-Fe-content Fe-Co-B-C-Si-Cu amorphous alloys by minor doping of Cu gives a guideline to developing high Bs amorphous alloys with excellent AFA.
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Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits
NASA Astrophysics Data System (ADS)
Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao
2015-11-01
The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.
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NASA Astrophysics Data System (ADS)
Roh, Y.; Oh, J.; Seo, H.; Rhee, S.
2007-12-01
The Underground Research Tunnel (URT) located in Korea Atomic Energy Research Institute (KAERI), Daejeon, South Korea was recently constructed as an experimental site to study radionuclide transport, biogeochemistry, radionuclide-mineral interactions for the geological disposal of high level nuclear waste. Groundwater sampled from URT was used to examine microbial diversity and to enrich metal reducing bacteria for studying microbe- metal interactions. Genomic analysis indicated that the groundwater contained diverse microorganisms such as metal reducers, metal oxidizers, anaerobic denitrifying bacteria, and bacteria for reductive dechlorination. Metal- reducing bacteria enriched from the groundwater was used to study metal reduction and biomineralization. The metal-reducing bacteria enriched with acetate or lactate as the electron donors showed the bacteria reduced Fe(III)-citrate, Fe(III) oxyhydroxides, Mn(IV) oxide, and Cr(VI) as the electron acceptors. Preliminary study indicated that the enriched bacteria were able to use glucose, lactate, acetate, and hydrogen as electron donors while reducing Fe(III)-citrate or Fe(III) oxyhydroxide as the electron acceptor. The bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite, siderite, and rhodochrosite. The results indicated that Fe(III)- and metal-reducing communities are present in URT at the KAERI.
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Ott, N; Beni, A; Ulrich, A; Ludwig, C; Schmutz, P
2014-03-01
Al-Cr-Fe complex metallic alloys are new intermetallic phases with low surface energy, low friction, and high corrosion resistance down to very low pH values (0-2). Flow microcapillary plasma mass spectrometry under potentiostatic control was used to characterize the dynamic aspect of passivation of an Al-Cr-Fe gamma phase in acidic electrolytes, allowing a better insight on the parameters inducing chemical stability at the oxyhydroxide-solution interface. In sulfuric acid pH 0, low element dissolution rates (in the µg cm(-2) range after 60 min) evidenced the passive state of the Al-Cr-Fe gamma phase with a preferential over-stoichiometric dissolution of Al and Fe cations. Longer air-aging was found to be beneficial for stabilizing the passive film. In chloride-containing electrolytes, ten times higher Al dissolution rates were detected at open-circuit potential (OCP), indicating that the spontaneously formed passive film becomes unstable. However, electrochemical polarization at low passive potentials induces electrical field generated oxide film modification, increasing chemical stability at the oxyhydroxide-solution interface. In the high potential passive region, localized attack is initiated with subsequent active metal dissolution. © 2013 Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
Préat, A.; Mamet, B.; Di Stefano, P.; Martire, L.; Kolo, K.
2011-06-01
This article presents a petrographic comparison of the Rosso Ammonitico facies of Western Sicily and the original Rosso Ammonitico Veronese of Northern Italy based on a total of 27 sections. The Rosso Ammonitico has been the subject of numerous controversies that range from bathyal to shallow-water platform sedimentation. Therefore it seemed interesting to verify if the term Rosso Ammonitico has the same geologic connotation from region to region. The Middle-Upper Jurassic Rosso Ammonitico of Western Sicily is a condensed succession formed during a period of extensional synsedimentary tectonics related to the spreading of the Ionian Ocean. Slope-to-basin or pelagic carbonate deposits characterize the sedimentation which consists of reddish mudstones and wackestones. The abundant fauna is composed of radiolarians, protoglobigerinids, Saccocoma, Bositra associated with ammonites. A few ferruginous hardgrounds, Fe-Mn oxide crusts and Mn-coated condensation horizons are also present. The red matrices contain abundant Fe-Mn encrusted, microbored and bioeroded bioclasts. Sporadic Fe-Mn oncolites composed of amorphous Mn-minerals and goethite are also conspicuous. The matrix, as well as the shells and the fillings of the complex associated veinlets, are frequently altered into calcite microsparite. Submicronic iron bacterial and fungal filaments associated with mineralized extracellular polymeric substances (EPS) are observed in the matrix. They record dysaerobic microenvironments at or near the sediment-water interfaces. Early mineralized discontinuities enhanced by subsequent pressure dissolution are reported in the succession. Mn-(Ni) bacterial filaments are exceptionally observed in the cortex of the Fe-Mn oncolites. As a consequence of an early lithification, the Mn filaments are poorly preserved. The pigmentation of the rock is due to the dispersion of submicronic oxyhydroxides (now goethite and amorphous iron) formed by bacterial mediation during early diagenesis in microaerophilitic environments. As in the case of the original 'Rosso Ammonitico Veronese', Fe and Mn bacteria/fungi were able to produce bioconstructions which have no bathymetric significance. The limiting factor must have been the oxygen content which was low in these very quiet and relatively deep environments. Thus the Rosso Ammonitico of northern and southern Italy have a number of points in common, but some obvious dissimilarities are observed that explain some of the various sedimentological interpretations. Among them, the chemical composition is of particular importance, more Fe is present in Veneto (Northern Italy) while Mn is associated with the Sicilian Rosso Ammonitico. The Sicilian localities were more proximal to oceanic magmatic sources which were related to the activity of the oceanic crust.
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Usher, Courtney R; Cleveland, Curtis A; Strongin, Daniel R; Schoonen, Martin A
2004-11-01
FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.
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Bacterial nanometric amorphous Fe-based oxide: a potential lithium-ion battery anode material.
Hashimoto, Hideki; Kobayashi, Genki; Sakuma, Ryo; Fujii, Tatsuo; Hayashi, Naoaki; Suzuki, Tomoko; Kanno, Ryoji; Takano, Mikio; Takada, Jun
2014-04-23
Amorphous Fe(3+)-based oxide nanoparticles produced by Leptothrix ochracea, aquatic bacteria living worldwide, show a potential as an Fe(3+)/Fe(0) conversion anode material for lithium-ion batteries. The presence of minor components, Si and P, in the original nanoparticles leads to a specific electrode architecture with Fe-based electrochemical centers embedded in a Si, P-based amorphous matrix.
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Dose dependence of radiation damage in nano-structured amorphous SiOC/crystalline Fe composite
Su, Qing; Price, Lloyd; Shao, Lin; ...
2015-10-29
Here, through examination of radiation tolerance properties of amorphous silicon oxycarbide (SiOC) and crystalline Fe composite to averaged damage levels, from approximately 8 to 30 displacements per atom (dpa), we demonstrated that the Fe/SiOC interface and the Fe/amorphous Fe xSi yO z interface act as efficient defect sinks and promote the recombination of vacancies and interstitials. For thick Fe/SiOC multilayers, a clear Fe/SiOC interface remained and no irradiation-induced mixing was observed even after 32 dpa. For thin Fe/SiOC multilayers, an amorphous Fe xSi yO z intermixed layer was observed to form at 8 dpa, but no further layer growth wasmore » observed for higher dpa levels.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hall, James A.; Mailloux, Brian J.; Onstott, Tullis C.
2005-02-01
Twenty eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7 cm long columns of intact sediment or re-packed sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of the columns to examine the effect of cellmore » morphology and surface properties on bacterial transport. The effect of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also delineated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide coated columns, but only in the sub-oxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect is profound for weakly charged, hydrophilic bacteria and may contribute to differences in observations between laboratory experiments verses field-scale investigations particularly if the groundwater pH remains circum-neutral and Fe oxyhydroxide phases exist. These observations validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Moncur, Michael C.; Paktunc, Dogan; Jean Birks, S.
Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrationsmore » in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(-I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.« less
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Chen, Ying-Chu; Lin, Yan-Gu; Hsu, Yu-Kuei; Yen, Shi-Chern; Chen, Kuei-Hsien; Chen, Li-Chyong
2014-09-24
A simple one-step electroplating route is proposed for the synthesis of novel iron oxyhydroxide lepidocrocite (γ-FeOOH) nanosheet anodes with distinct layered channels, and the microstructural influence on the pseudocapacitive performance of the obtained γ-FeOOH nanosheets is investigated via in situ X-ray absorption spectroscopy (XAS) and electrochemical measurement. The in situ XAS results regarding charge storage mechanisms of electrodeposited γ-FeOOH nanosheets show that a Li(+) can reversibly insert/desert into/from the 2D channels between the [FeO6 ] octahedral subunits depending on the applied potential. This process charge compensates the Fe(2+) /Fe(3+) redox transition upon charging-discharging and thus contributes to an ideal pseudocapacitive behavior of the γ-FeOOH electrode. Electrochemical results indicate that the γ-FeOOH nanosheet shows the outstanding pseudocapacitive performance, which achieves the extraordinary power density of 9000 W kg(-1) with good rate performance. Most importantly, the asymmetric supercapacitors with excellent electrochemical performance are further realized by using 2D MnO2 and γ-FeOOH nanosheets as cathode and anode materials, respectively. The obtained device can be cycled reversibly at a maximum cell voltage of 1.85 V in a mild aqueous electrolyte, further delivering a maximum power density of 16 000 W kg(-1) at an energy density of 37.4 Wh kg(-1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Xiao, Shifang; Li, Xiaofan; Deng, Huiqiu; Deng, Lei; Hu, Wangyu
2015-03-07
Despite an intensive investigation on bimetallic nanoparticles, little attention has been paid to their amorphization in the past few decades. The study of amorphization on a nanoscale is of considerable significance for the preparation of amorphous nanoparticles and bulk metallic glass. Herein, we pursue the amorphization process of Al-based nanoparticles with classic molecular dynamics simulations and local structural analysis techniques. By a comparative study of the amorphization of pure Al and Fe-doped Al-based nanodroplets in the course of rapid cooling, we find that Fe addition plays a very important role in the vitrification of Al-based nanodroplets. Owing to the subsurface segregated Fe atoms with their nearest neighbors tending to form relatively stable icosahedral (ICO) clusters, the Fe-centred cluster network near the surface effectively suppresses the crystallization of droplets from surface nucleation and growth as the concentration of Fe attains a certain value. The glass formation ability of nanodroplets is suggested to be enhanced by the high intrinsic inner pressure as a result of small size and surface tension, combined with the dopant-inhibited surface nucleation. In addition, the effect of the size and the added concentration of nanoparticles on amorphization and the thermal stability of the amorphous nanoparticles are discussed. Our findings reveal the amorphization mechanism in Fe-doped Al-based nanoparticles and provide a theoretical guidance for the design of amorphous materials.
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Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan
2014-01-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.
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Yang, Qiang; Culbertson, Charles W; Nielsen, Martha G; Schalk, Charles W; Johnson, Carole D; Marvinney, Robert G; Stute, Martin; Zheng, Yan
2015-02-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 mg/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ(18)O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. Copyright © 2014 Elsevier B.V. All rights reserved.
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Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan
2014-01-01
To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 µg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70–100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93–99%) in particulates (>0.45 µm). These particulates and those settled after a 16-day batch experiment contain 560–13,000 mg/kg of As and 14–35% weight/weight of Fe. As/Fe ratios (2.5–20 mmole/mole) and As partitioning ratios (adsorbed/dissolved [As], 20,000–100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1,300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. PMID:24842411
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NASA Astrophysics Data System (ADS)
Villanova-de-Benavent, Cristina; Domènech, Cristina; Tauler, Esperança; Galí, Salvador; Tassara, Santiago; Proenza, Joaquín A.
2017-10-01
Fe-Ni-bearing serpentine from the saprolite horizon is the main Ni ores in hydrous silicate-type Ni laterites and formed by chemical weathering of partially serpentinized ultramafic rocks under tropical conditions. During lateritization, Mg, Si, and Ni are leached from the surface and transported downwards. Fe2+ is oxidized to Fe3+ and fixed as insoluble Fe-oxyhydroxides (mostly goethite) that incorporate Ni. This Ni is later leached from goethite and incorporated in secondary serpentine and garnierite. As a result, a serpentine-dominated saprolite horizon forms over the ultramafic protolith, overlapped by a Fe-oxyhydroxide-dominated limonite horizon. The serpentine from the protolith (serpentine I) is of hydrothermal origin and yields similar Ni (0.10-0.62 wt.% NiO) and lower Fe (mostly 1.37-5.81 wt.% FeO) concentrations than the primary olivine. In contrast, Fe-Ni-bearing serpentine from the saprolite (serpentine II) shows significantly higher and variable Fe and Ni contents, typically ranging from 2.23 to 15.59 wt.% Fe2O3 and from 1.30 to 7.67 wt.% NiO, suggesting that serpentine get enriched in Fe and Ni under supergene conditions. This study presents detailed mineralogical, textural, and chemical data on this serpentine II, as well as new insights by thermodynamic calculations assuming ideal solution between Fe-, Ni- and Mg-pure serpentines. The aim is to assess if at atmospheric pressure and temperature Fe-Ni-bearing serpentine can be formed by precipitation. Results indicate that the formation of serpentine II under atmospheric pressure and temperature is thermodynamically supported, and pH, Eh, and the equilibrium constant of the reaction are the parameters that affect the results more significantly.
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Elevated arsenic and manganese in groundwaters of Murshidabad, West Bengal, India.
Sankar, M S; Vega, M A; Defoe, P P; Kibria, M G; Ford, S; Telfeyan, K; Neal, A; Mohajerin, T J; Hettiarachchi, G M; Barua, S; Hobson, C; Johannesson, K; Datta, S
2014-08-01
High levels of geogenic arsenic (As) and manganese (Mn) in drinking water has led to widespread health problems for the population of West Bengal, India. Here we delineate the extent of occurrences of As and Mn in Murshidabad, where the contaminated aquifers occur at shallow depths between 35 and 40 m and where access to safe drinking water is a critical issue for the local population. A total of 78 well-water samples were taken in 4 blocks on either side of the river Bhagirathi: Nabagram and Kandi (west, Pleistocene sediments), Hariharpara and Beldanga (east, Holocene sediments). High As, total iron (FeT) and low Mn concentrations were found in waters from the Holocene gray sediment aquifers east of the river Bhagirathi, while the opposite was found in the Pleistocene reddish-brown aquifer west of the river Bhagirathi in Murshidabad. Speciation of As in water samples from Holocene sediments revealed the dominant species to be As(III), with ratios of As(III):AsT ranging from 0.55 to 0.98 (average 0.74). There were indications from saturation index estimations that Mn solubility is limited by the precipitation of MnCO3. Tubewells from high As areas in proximity to anthropogenic waste influx sources showing high molar Cl/Br ratios, low SO4(2-) and low NO3(-) demonstrate relatively lower As concentrations, thereby reducing As pollution in those wells. Analyses of core samples (2 in each of the blocks) drilled to a depth of 45 m indicate that there is no significant variation in bulk As (5-20mg/kg) between the Holocene and Pleistocene sediments, indicating that favorable subsurface redox conditions conducive to mobilization are responsible for the release of As. The same applies to Mn, but concentrations vary more widely (20-2000 mg/kg). Sequential extraction of Holocene sediments showed As to be associated with 'specifically sorbed-phosphate-extractable' phases (10-15%) and with 'amorphous and well crystalline Fe-oxyhydroxide' phases (around 37%) at As-contaminated well depths, suggesting that the main As release mechanisms could be either competitive ion exchange with PO4(3-), or the dissolution of Fe oxyhydroxides. In the Pleistocene sediments Mn is predominantly found in the easily exchangeable fraction. Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
Johannessen, Karen C.; Vander Roost, Jan; Dahle, Håkon; Dundas, Siv H.; Pedersen, Rolf B.; Thorseth, Ingunn H.
2017-04-01
Diffuse low-temperature hydrothermal vents on the seafloor host neutrophilic microaerophilic Fe-oxidizing bacteria that utilize the Fe(II) supplied by hydrothermal fluids and produce intricate twisted and branching extracellular stalks. The growth behavior of Fe-oxidizing bacteria in strongly opposing gradients of Fe(II) and O2 have been thoroughly investigated in laboratory settings to assess whether extracellular stalks and aligned biomineralized fabrics may serve as biosignatures of Fe-oxidizing bacteria and indications of palaeo-redox conditions in the rock record. However, the processes controlling the growth of biogenic Fe-oxyhydroxide deposits in natural, modern hydrothermal systems are still not well constrained. In this study, we aimed to establish how variations in the texture of stratified hydrothermal Fe-oxyhydroxide deposits are linked to the physicochemical conditions of the hydrothermal environment. We conducted 16S rRNA gene analyses, microscopy and geochemical analyses of laminated siliceous Fe-mounds from the Jan Mayen Vent Fields at the Arctic Mid-Ocean Ridge. Chemical analyses of low- and high-temperature hydrothermal fluids were performed to characterize the hydrothermal system in which the Fe-deposits form. Our results reveal synchronous inter-laminar variations in texture and major and trace element geochemistry. The Fe-deposits are composed of alternating porous laminae of mineralized twisted stalks and branching tubes, Mn-rich horizons with abundant detrital sediment, domal internal cavities and thin P- and REE-enriched lamina characterized by networks of ≪1 μm wide fibers. Zetaproteobacteria constitute one third of the microbial community in the surface layer of actively forming mounds, indicating that microbial Fe-oxidation is contributing to mound accretion. We suggest that Mn-oxide precipitation and detrital sediment accumulation take place during periodically low hydrothermal fluid discharge conditions. The elevated concentrations of P and REE in distinct laminae suggest Fe-cycling and accumulation of diagenetic species at depth in the deposits during hydrothermal quiescence and co-precipitation of these species with Fe-oxyhydroxides at the mound surface with reinitiated hydrothermal discharge. The origin of the low-temperature hydrothermal source fluid and the Fe-deposits are evident by low LREE/HREE ratios and negative Eu-anomalies, which clearly differ from the LREE and Eu enrichment of nearby high-temperature white smoker venting fluids. Our study demonstrates that hydrothermal fluctuations exert the primary control on the formation of laminae and the activity of Fe-oxidizing bacteria in marine hydrothermal Fe-deposits and indicates that REE-patterns may be used to distinguish high-temperature plume fallout and biomineralized low-temperature Fe-deposits in the rock record.
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Chakraborty, Parthasarathi; Chakraborty, Sucharita; Jayachandran, Saranya; Madan, Ritu; Sarkar, Arindam; Linsy, P; Nath, B Nagender
2016-10-01
This study describes the effect of varying bottom-water oxygen concentration on geochemical fractionation (operational speciation) of Cu and Pb in the underneath sediments across the oxygen minimum zone (Arabian Sea) in the west coast of India. Both, Cu and Pb were redistributed among the different binding phases of the sediments with changing dissolved oxygen level (from oxic to hypoxic and close to suboxic) in the bottom water. The average lability of Cu-sediment complexes gradually decreased (i.e., stability increased) with the decreasing dissolved oxygen concentrations of the bottom water. Decreasing bottom-water oxygen concentration increased Cu association with sedimentary organic matter. However, Pb association with Fe/Mn-oxyhydroxide phases in the sediments gradually decreased with the decreasing dissolved oxygen concentration of the overlying bottom water (due to dissolution of Fe/Mn oxyhydroxide phase). The lability of Pb-sediment complexes increased with the decreasing bottom-water oxygen concentration. This study suggests that bottom-water oxygen concentration is one of the key factors governing stability and lability of Cu and Pb complexes in the underneath sediment. Sedimentary organic matter and Fe/Mn oxyhydroxide binding phases were the major hosting phases for Cu and Pb respectively in the study area. Increasing lability of Pb-complexes in bottom sediments may lead to positive benthic fluxes of Pb at low oxygen environment. Copyright © 2016 Elsevier B.V. All rights reserved.
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Silva, Veronica; Loredo, Jorge; Fernández-Martínez, Rodolfo; Larios, Raquel; Ordóñez, Almudena; Gómez, Belén; Rucandio, Isabel
2014-10-01
Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80% of total As.
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Biswas, Ashis; Gustafsson, Jon Petter; Neidhardt, Harald; Halder, Dipti; Kundu, Amit K; Chatterjee, Debashis; Berner, Zsolt; Bhattacharya, Prosun
2014-05-15
This study assesses the role of competing ions in the mobilization of arsenic (As) by surface complexation modeling of the temporal variability of As in groundwater. The potential use of two different surface complexation models (SCMs), developed for ferrihydrite and goethite, has been explored to account for the temporal variation of As(III) and As(V) concentration, monitored in shallow groundwater of Bengal Basin over a period of 20 months. The SCM for ferrihydrite appears as the better predictor of the observed variation in both As(III) and As(V) concentrations in the study sites. It is estimated that among the competing ions, PO4(3-) is the major competitor of As(III) and As(V) adsorption onto Fe oxyhydroxide, and the competition ability decreases in the order PO4(3-) ≫ Fe(II) > H4SiO4 = HCO3(-). It is further revealed that a small change in pH can also have a significant effect on the mobility of As(III) and As(V) in the aquifers. A decrease in pH increases the concentration of As(III), whereas it decreases the As(V) concentration and vice versa. The present study suggests that the reductive dissolution of Fe oxyhydroxide alone cannot explain the observed high As concentration in groundwater of the Bengal Basin. This study supports the view that the reductive dissolution of Fe oxyhydroxide followed by competitive sorption reactions with the aquifer sediment is the processes responsible for As enrichment in groundwater. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Sequestration of Tellurium From Seawater by Ferromanganese Crusts: A XANES/EXAFS Perspective
NASA Astrophysics Data System (ADS)
Hein, J. R.; Bargar, J.; Koschinsky, A.; Dunham, R.; Halliday, A. N.
2007-12-01
Marine iron-oxyhydroxide/manganese-oxide crusts (Fe-Mn crusts) provide the richest known source of tellurium (Te). Te averages about 50 ppm in Fe-Mn crusts distributed globally, with concentrations locally up to 210 ppm. The sorption of Te onto Fe-Mn crusts likely controls the dominant redox species and concentration of Te in the global ocean (Hein et al., 2003). However, little is known about the mechanisms by which Te is sequestered by Fe-Mn crusts and Fe-Mn colloids in the water column, and then stabilized in the Fe/Mn oxyhydroxide/oxide framework. Two primary hypotheses are being tested: (a) Te(IV) is initially the predominant adsorbed species, which is subsequently oxidized on the Fe-oxyhydroxide and/or Mn oxide phases in natural systems and in sorption experiments. (b) Once oxidized, Te(VI) remains tightly bound to the Fe phase in Fe-Mn crusts as adsorbed surface complexes. These hypotheses are being examined by using the Stanford Synchrotron Radiation Laboratory's (SSRL) synchrotron-based XANES (x-ray absorption near-edge structure) spectroscopy to assess Te oxidation state in natural samples and samples in which Te(IV) and Te(VI) were sorbed onto synthetic and natural FeOOH and Mn oxides. EXAFS (extended x-ray absorption fine structure) spectroscopy is being used to resolve the local molecular-scale structure around Te in these same samples. Data have thus far been obtained for six Fe-Mn crusts from a variety of geographic locations and water depths of occurrence, with differing chemical compositions; and two model compounds, Te(IV) sorbed on FeOOH and Te(IV) sorbed on MnO2. XANES data show that for all six Fe-Mn crust samples, 85 to 100 percent of the Te occurs as Te(VI). For the model compounds, about 65 percent of the Te(IV) sorbed onto the MnO2 had oxidized to Te(VI) by the time (one week) the sample was analyzed, whereas Te sorbed onto FeOOH remained at about 100 percent Te(IV). The most striking result from the EXAFS data is that all spectra for the six Fe-Mn crust samples are virtually identical, regardless of location, depositional conditions, or chemical and mineralogical compositions. This uniformity indicates that the local structure around Te is similar for all samples and, therefore, the mode of incorporation of Te into the Fe-Mn crusts does not vary despite varying environments of formation. This implies that a single set of processes applies throughout the global ocean to the incorporation of Te into Fe-Mn crusts. Hein, J.R., Koschinsky, A., and Halliday, A.N., 2003, Geochim. Cosmochim. Acta 67: 1117-1127.
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Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings.
Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A H
2015-01-01
Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal.
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Extremely High Phosphate Sorption Capacity in Cu-Pb-Zn Mine Tailings
Huang, Longbin; Li, Xiaofang; Nguyen, Tuan A. H.
2015-01-01
Elevated inorganic phosphate (Pi) concentrations in pore water of amended tailings under direct revegetation may cause toxicity in some native woody species but not native forbs or herb species, all of which are key constituents in target native plant communities for phytostabilizing base metal mine tailings. As a result, Pi sorption capacity has been quantified by a conventional batch procedure in three types of base metal mine tailings sampled from two copper (Cu)-lead (Pb)-zinc (Zn) mines, as the basis for Pi-fertiliser addition. It was found that the Pi-sorption capacity in the tailings and local soil was extremely high, far higher than highly weathered agricultural soils in literature, but similar to those of volcanic ash soils. The Langmuir P-sorption maximum was up to 7.72, 4.12, 4.02 and 3.62 mg P g-1 tailings, in the fresh tailings of mixed Cu-Pb-Zn streams (MIMTD7), the weathered tailings of mixed Cu-Pb-Zn streams (MIMTD5), EHM-TD (fresh Cu-stream, high magnetite content) and local soil (weathered shale and schist), respectively. Physicochemical factors highly correlated with the high Pi-sorption in the tailings were fine particle distribution, oxalate and dithionite-citrate-bicarbonate extractable Fe (FeO and Fed), oxalate-extractable Al and Mn, and the levels of soluble Cd and Zn, and total S and Fe. Large amounts of amorphous Fe oxides and oxyhydroxides may have been formed from the oxidation of pyritic materials and redox cycles of Fe-minerals (such as pyrite (FeS2), ankerite (Ca(Fe Mg)(CO3)2 and siderite (FeCO3), as indicated by the extractable FeO values. The likely formation of sparingly soluble Zn-phosphate in the Pb-Zn tailings containing high levels of Zn (from sphalerite ((Zn,Fe)S, ZnS, (Zn,Cd)S)) may substantially lower soluble Zn levels in the tailings through high rates of Pi-fertiliser addition. As a result, the possibility of P-toxicity in native plant species caused by the addition of soluble phosphate fertilizers would be minimal. PMID:26295582
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Trace Uranium Partitioning in a Multiphase Nano-FeOOH System.
McBriarty, Martin E; Soltis, Jennifer A; Kerisit, Sebastien; Qafoku, Odeta; Bowden, Mark E; Bylaska, Eric J; De Yoreo, James J; Ilton, Eugene S
2017-05-02
The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH) 3 ] to nanoparticulate iron oxyhydroxide minerals in the presence of uranyl (UO 2 ) 2+ (aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.
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Pichler, T.; Ridley, W.I.; Nelson, E.
1999-01-01
A suite of submarine volcanic rocks from the Southern Chile Ridge has been examined in order to investigate the early stages of low temperature alteration. Alteration in these samples proceeded as follows: (1) Fe-staining on sample surface and along fractures, (2) filling of vesicles with secondary material, (3) breakdown of glassy matrix, (4) breakdown of microcrystalline matrix, and (5) breakdown and replacement of olivine. Plagioclase and pyroxene were sometimes found to be slightly altered along internal fissures. Secondary or alteration phases generally showed high K (3-5 wt.%), Fe (30-70 wt.%) and low Al ( Rb > K. During initial stages of alteration the behavior of some trace elements such as rare-earth elements (REE), Ba, Zr, Hf, Ta, Nb, and Mo are solely controlled by the precipitation of Mn-rich Fe-oxyhydroxides. The preferred incorporation of Ce into Mn-rich Fe-oxyhydroxides may be a principal factor explaining the Ce depletion in seawater. We conclude that the earliest stages of submarine weathering are controlled by Eh and pH gradients between the rock and seawater. In the absence of a buffer, oxidation of ferrous iron causes a decrease in solution pH.
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Trace Uranium Partitioning in a Multiphase Nano-FeOOH System
DOE Office of Scientific and Technical Information (OSTI.GOV)
McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien
The characterization of trace elements in minerals using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities and contaminants interact with the host phase and the environment. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic actinides. The reductive transformation of ferrihydrite [Fe(OH)3] to nanoparticulate iron oxyhydroxide minerals in themore » presence of uranyl (UO 2) 2+(aq) resulted in the preferential incorporation of U into goethite (α-FeOOH) over lepidocrocite (γ-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. We demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations and uncertainty of traditional shell-by-shell EXAFS fitting, enabling the detailed characterization of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multiphase mineral systems.« less
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Trace Uranium Partitioning in a Multiphase Nano-FeOOH System
DOE Office of Scientific and Technical Information (OSTI.GOV)
McBriarty, Martin E.; Soltis, Jennifer A.; Kerisit, Sebastien
The characterization of trace elements in nanomaterials using extended X-ray absorption fine structure (EXAFS) spectroscopy constitutes a first step toward understanding how impurities or dopants affect the properties of the host phase. However, limitations to EXAFS interpretation complicate the analysis of trace concentrations of impurities that are distributed across multiple phases in a heterogeneous system. Ab initio molecular dynamics (AIMD)-informed EXAFS analysis was employed to investigate the immobilization of trace uranium associated with nanophase iron (oxyhydr)oxides, a model system for the geochemical sequestration of radiotoxic contaminants. The reductive transformation of ferrihydrite (Fe(OH)3) to nano-particulate iron oxyhydroxide minerals in the presencemore » of uranyl (UO2)2+(aq) resulted in the preferential incorporation of U into goethite (a-FeOOH) over lepidocrocite (g-FeOOH), even though reaction conditions favored the formation of excess lepidocrocite. This unexpected result is supported by atomically resolved transmission electron microscopy. Using this model system, we demonstrate how AIMD-informed EXAFS analysis lifts the strict statistical limitations of traditional shell-by-shell EXAFS modeling, enabling the detailed analysis of the local bonding environment, charge compensation mechanisms, and oxidation states of polyvalent impurities in complex multi-phase nano-systems.« less
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The effects of redox fluctuation on iron-organic matter interactions in wet tropical soils
NASA Astrophysics Data System (ADS)
Bhattacharyya, A.; Campbell, A.; Lin, Y.; Nico, P. S.; Silver, W. L.; Pett-Ridge, J.
2016-12-01
Two-thirds of the C in the terrestrial biosphere is stored as soil organic C, and much of this is stabilized via iron (Fe) mineral-organic matter (OM) associations that are susceptible to redox effects. The rapid C cycling typical of wet tropical ecosystems- driven by ample moisture and temperature- may also be fueled by a characteristically dynamic redox environment. Yet the net result of altered tropical soil climate and fluctuating soil redox regimes on Fe-organic matter associations is poorly understood. In this study, we hypothesized that the timing of redox transitions (frequency of O2 introduction and ferrous iron (Fe2+) generation) will lead to differences in Fe (oxyhydr)oxide mineral crystallinity and C degradation rates and alter the proportion of organic C associated with iron minerals. Surface soils from a humid tropical forest in Puerto Rico were incubated for 44 days under four redox regimes: (1) static anoxic, (2) static oxic, (3) 4 days anoxic, 4 days oxic, and (4) 4 days anoxic, 8 days oxic. Replicate microcosms were harvested at multiple time points, including before and after a redox switch (oxic to anoxic or vice versa). Selective chemical extractions, bulk Fe K-edge EXAFS and STXM/NEXAFS spectromicroscopy were used to comprehensively probe treatment effects on Fe and C speciation. Static redox conditions had a significant effect on Fe2+ and dissolved organic carbon (DOC) concentrations, and prolonged anoxia promoted reductive dissolution of Fe-oxides and an increase in amorphous or short-range ordered (SRO) Fe oxides. Preferential dissolution of this less-crystalline Fe pool was more prominent during rapid redox switches from oxic to anoxic conditions, and coincided with increased DOC. Bulk Fe K-edge EXAFS spectroscopy identified Fe3+ as the dominant Fe species in all treatments and indicated O/N atoms in the first Fe co-ordination sphere and features similar to SRO Fe-oxide phases (e.g. ferrihydrite or nano-goethite) in the second co-ordination sphere. STXM/NEXAFS analyses indicated an increase in lignin-like biomolecules under static anoxic conditions, and a potential role of Fe-lignin interactions under strong reducing conditions. Our current findings highlight the necessity to explore natural redox-dynamic systems in greater detail in order to develop a better model for climate change.
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Poigner, Harald; Wilhelms-Dick, Dorothee; Abele, Doris; Staubwasser, Michael; Henkel, Susann
2015-09-01
Iron stable isotope signatures (δ(56)Fe) in hemolymph (bivalve blood) of the Antarctic bivalve Laternula elliptica were analyzed by Multiple Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) to test whether the isotopic fingerprint can be tracked back to the predominant sources of the assimilated Fe. An earlier investigation of Fe concentrations in L. elliptica hemolymph suggested that an assimilation of reactive and bioavailable Fe (oxyhydr)oxide particles (i.e. ferrihydrite), precipitated from pore water Fe around the benthic boundary, is responsible for the high Fe concentration in L. elliptica (Poigner et al., 2013 b). At two stations in Potter Cove (King George Island, Antarctica) bivalve hemolymph showed mean δ(56)Fe values of -1.19 ± 0.34‰ and -1.04 ± 0.39 ‰, respectively, which is between 0.5‰ and 0.85‰ lighter than the pool of easily reducible Fe (oxyhydr)oxides of the surface sediments (-0.3‰ to -0.6‰). This is in agreement with the enrichment of lighter Fe isotopes at higher trophic levels, resulting from the preferential assimilation of light isotopes from nutrition. Nevertheless, δ(56)Fe hemolymph values from both stations showed a high variability, ranging between -0.21‰ (value close to unaltered/primary Fe(oxyhydr)oxide minerals) and -1.91‰ (typical for pore water Fe or diagenetic Fe precipitates), which we interpret as a "mixed" δ(56)Fe signature caused by Fe assimilation from different sources with varying Fe contents and δ(56)Fe values. Furthermore, mass dependent Fe fractionation related to physiological processes within the bivalve cannot be ruled out. This is the first study addressing the potential of Fe isotopes for tracing back food sources of bivalves. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Characteristics and origin of rock varnish from the hyperarid coastal deserts of northern Peru
NASA Astrophysics Data System (ADS)
Jones, Charles E.
1991-01-01
The characteristics of a new type of rock varnish from the hyperarid coastal deserts of northern Peru, combined with laboratory experiments on associated soil materials, provide new insights into the formation of rock varnish. The Peruvian varnish consists of an Fe-rich, Mn-poor component covering up to 95% of a varnished surface and a Fe-rich, Mn-rich component found only in pits and along cracks and ridges. The alkaline soils plus the catalytic Fe oxyhydroxides that coat much of the varnish surfaces make the Peruvian situation ideal for physicochemical precipitation of Mn. However, the low Mn content of the dominant Fe-rich, Mn-poor component suggests that such precipitation is minor. This, plus the presence of abundant bacteria in the Mn-rich varnish and the recorded presence of Mn-precipitating bacteria in varnish elsewhere, suggests that bacteria are almost solely responsible for Mn-precipitation in rock varnish. A set of experiments involving Peruvian soil samples in contact with water-CO 2 solutions indicates that natural fogs or dews release Mn but not Fe when they come in contact with eolian materials on rock surfaces. This mechanism may efficiently provide Mn to bacteria on varnishing surfaces. The lack of Fe in solution suggests that a large but unknown proportion of Fe in varnish may be in the form of insoluble Fe oxyhydroxides sorbed onto the clay minerals that form the bulk of rock varnish. The results of this study do not substantively change R. I. Dorn's paleoenvironmental interpretations of varnish Mn:Fe ratios, but they do suggest areas for further inquiry.
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NASA Astrophysics Data System (ADS)
Foster, A. L.; Klofas, J. M.; Hein, J. R.; Koschinsky, A.; Bargar, J.; Dunham, R. E.; Conrad, T. A.
2011-12-01
Marine ferromanganese crusts and nodules ("Fe-Mn crusts") are considered a potential mineral resource due to their accumulation of several economically-important elements at concentrations above mean crustal abundances. They are typically composed of intergrown Fe oxyhydroxide and Mn oxide; thicker (older) crusts can also contain carbonate fluorapatite. We used X-ray absorption fine-structure (XAFS) spectroscopy, a molecular-scale structure probe, to determine the speciation of several elements (Te, Bi, Mo, Zr, Pt) in Fe-Mn crusts. As a first step in analysis of this dataset, we have conducted principal component analysis (PCA) of Te K-edge and Mo K-edge, k3-weighted XAFS spectra. The sample set consisted of 12 homogenized, ground Fe-Mn crust samples from 8 locations in the global ocean. One sample was subjected to a chemical leach to selectively remove Mn oxides and the elements associated with it. The samples in the study set contain 50-205 mg/kg Te (average = 88) and 97-802 mg/kg Mo (average = 567). PCAs of background-subtracted, normalized Te K-edge and Mo K-edge XAFS spectra were performed on a data matrix of 12 rows x 122 columns (rows = samples; columns = Te or Mo fluorescence value at each energy step) and results were visualized without rotation. The number of significant components was assessed by the Malinowski indicator function and ability of the components to reconstruct the features (minus noise) of all sample spectra. Two components were significant by these criteria for both Te and Mo PCAs and described a total of 74 and 75% of the total variance, respectively. Reconstruction of potential model compounds by the principal components derived from PCAs on the sample set ("target transformation") provides a means of ranking models in terms of their utility for subsequent linear-combination, least-squares (LCLS) fits (the next step of data analysis). Synthetic end-member models of Te4+, Te6+, and Mo adsorbed to Fe(III) oxyhydroxide and Mn oxide were tested. Te6+ sorbed to Fe oxyhydroxide and Mo sorbed to Fe oxyhydroxide were identified as the best models for Te and Mo PCAs, respectively. However, in the case of Mo, least-squares fits contradicted these results, indicating that about 80% of Mo in crust samples was associated with Mn oxides. Ultimately it was discovered that the sample from which Mn oxide had been leached was skewing the results in the Mo PCA but not in the Te PCA. When the leached sample was removed and the Mo PCA repeated (n = 11), target transformation indicated that Mo sorbed to Mn oxide was indeed the best model for the set. Our results indicate that Te and Mo are strongly partitioned into different phases in these Fe-Mn crusts, and emphasize the importance of evaluating outliers and their effects on PCA.
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NASA Astrophysics Data System (ADS)
Choi, S. K.; Pak, S. J.; Kim, J.; Park, J. W.; Son, S. K.
2017-12-01
Sn-rich chimney fragments (up to 1,720 ppm) were recovered with ultramafic rocks from ocean core complex (OCC-4-1) of Central Indian Ridge, 12.4°S. The chimney fragments are featured by barite-free and Zn-rich (up to 50.1 wt.%) ores. The chimney fragments are mainly composed of sphalerite, isocubanite, pyrrhotite, chalcopyrite and marcasite with galena and electrum as minor minerals. The precipitation sequences of the minerals are categorized into three stages by mineral assemblage; early stage with low-temperature minerals, late stage with high-temperature minerals and seawater weathering stage with covellite, Fe-oxyhydroxides and amorphous silica. Early stage is characterized by sphalerite, intermittently showing colloform-texture, closely co-existed with anhedral marcasite and minor galena, whereas late stage is dominated by aggregates of isocubanite with chalcopyrite exsolution lamellae, pyrrhotite partially replaced by long prismatic marcasite and FeS enriched sphalerite (up to 42.69 FeS mole%). Electrums, main phase of gold mineralization, are mostly visible grains (< 3 um in diameter), occuring in sphalerite and isocubanite as inclusions and/or free gold in amorphous silica through the whole mineralization stages. On the basis of semi-quantified analysis, electrum grains are likely to have Au-rich composition. High Sn concentrations are typically observed in altered rim along the grain boundaries between sphalerite and isocubanite, going up to 5.5 wt.% in sphalerite. LA-ICP-MS mapping exhibits that Sn is preferentially incorporated into sphalerite relative to isocubanite, especially showing the highest values in boundaries between both minerals, but significantly lower in marcasite. Stoichiometry of Sn-enriched sphalerite rim seems to have a uniform ratio of atomic proportion of Cu to Sn as almost 2:1, implying that stannite micro-inclusions may result in Sn-enrichment. The LA-ICP-MS spectra also shows abrupt increase in Sn signal intensity, indicating Sn-bearing inclusions are distributed within sphalerite. Therefore, Sn-bearing mineral in sphalerite and isocubanite is likely to be fine particle of stannite in late stage and subsequently one of the possible ways to precipitate these particles could be reworking process of previously deposited Sn-bearing sulfides.
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Archeological Applications of XAFS: Prehistorical Paintings And Medieval Glasses
DOE Office of Scientific and Technical Information (OSTI.GOV)
Farges, F.; Chalmin, E.; Vignaud, C.
2006-10-27
High-resolution manganese and iron K-edges XANES spectra were collected on several samples of archeological interest: prehistorical paintings and medieval glasses. XANES spectra were collected at the ID21 facility (ESRF, Grenoble, France) using a micro-beam device and at the 11-2 beamline (SSRL, Stanford, USA) using a submillimetric beam. The medieval glasses studied are from gothic glass windows from Normandy (XIVth century). The aim of this study is to help understand the chemical durability of these materials, exposed to weathering since the XIVth century. They are used as analogues of weathered glasses used to dump metallic wastes. These glasses show surficial enrichmentmore » in manganese, due to its oxidation from II (glass) to III/IV (surface), which precipitates as amorphous oxy-hydroxides. Similarly, iron is oxidized on the surface and forms ferrihydrite-type aggregates. The prehistorical paintings are from Lascaux and Ekain (Basque country). We choose in that study the black ones, rich in manganese to search for potential evidences of some 'savoir-faire' that the Paleolithic men could have used to realize their paint in rock art, as shown earlier for Fe-bearing pigments. A large number of highly valuable samples, micrometric scaled, were extracted from these frescoes and show large variation in the mineralogical nature of the black pigments used, from an amorphous psilomelane-type to a well-crystallized pyrolusite. Correlation with the crystals morphology helps understanding the know-how of these early artists.« less
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Homogeneously dispersed, multimetal oxygen-evolving catalysts
Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; ...
2016-03-24
Earth-abundant first-row (3d) transition-metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials significantly above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxy-hydroxide materials with an atomically homogeneous metal distribution. These gelled FeCoW oxy-hydroxide exhibits the lowest overpotential (191 mV) reported at 10 mA per square centimeter in alkaline electrolyte. Here, the catalyst shows no evidence of degradation following more than 500 hours of operation. X-ray absorption and computationalmore » studies reveal a synergistic interplay between W, Fe and Co in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Saito, M.; Suzuki, S.; Kimura, M.
Quantitative X-ray structural analysis coupled with anomalous X-ray scattering has been used for characterizing the atomic-scale structure of rust formed on steel surfaces. Samples were prepared from rust layers formed on the surfaces of two commercial steels. X-ray scattered intensity profiles of the two samples showed that the rusts consisted mainly of two types of ferric oxyhydroxide, {alpha}-FeOOH and {gamma}-FeOOH. The amounts of these rust components and the realistic atomic arrangements in the components were estimated by fitting both the ordinary and the environmental interference functions with a model structure calculated using the reverse Monte Carlo simulation technique. The twomore » rust components were found to be the network structure formed by FeO{sub 6} octahedral units, the network structure itself deviating from the ideal case. The present results also suggest that the structural analysis method using anomalous X-ray scattering and the reverse Monte Carlo technique is very successful in determining the atomic-scale structure of rusts formed on the steel surfaces.« less
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NASA Astrophysics Data System (ADS)
Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin
2017-09-01
The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.
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Ferrofluids based on Co-Fe-Si-B amorphous nanoparticles
NASA Astrophysics Data System (ADS)
Wang, Tianqi; Bian, Xiufang; Yang, Chuncheng; Zhao, Shuchun; Yu, Mengchun
2017-03-01
Magnetic Co-Fe-Si-B amorphous nanoparticles were successfully synthesized by chemical reduction method. ICP, XRD, DSC, and TEM were used to investigate the composition, structure and morphology of Co-Fe-Si-B samples. The results show that the Co-Fe-Si-B samples are amorphous, which consist of nearly spherical nanoparticles with an average particle size about 23 nm. VSM results manifest that the saturation magnetization (Ms) of Co-Fe-Si-B samples ranges from 46.37 to 62.89 emu/g. Two kinds of ferrofluids (FFs) were prepared by dispersing Co-Fe-Si-B amorphous nanoparticles and CoFe2O4 nanoparticles in kerosene and silicone oil, respectively. The magnetic properties, stability and viscosity of the FFs were investigated. The FFs with Co-Fe-Si-B samples have a higher Ms and lower coercivity (Hc) than FFs with CoFe2O4 sample. Under magnetic field, the silicone oil-based FFs exhibit high stability. The viscosity of FFs under different applied magnetic fields was measured by a rotational viscometer, indicating that FFs with Co-Fe-Si-B particles present relative strong response to an external magnetic field. The metal-boride amorphous alloy nanoparticles have potential applications in the preparation of magnetic fluids with good stability and good magnetoviscous properties.
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THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.
2010-07-16
Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less thanmore » 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially in the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity in this site.« less
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The weathering of a sulfide orebody: Speciation and fate of some potential contaminants
Courtin-Nomade, A.; Grosbois, C.; Marcus, M.A.; Fakra, S.C.; Beny, J.-M.; Foster, A.L.
2009-01-01
Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogeni- cally modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., ??500 ??g/L Cu, ??3700 ??g/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 ??m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (??XAS), scanning X-ray diffraction ((??SXRD) and scanning X-ray fluorescence (??-SXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially at the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity at this site.
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NASA Astrophysics Data System (ADS)
Ma, Chung; Li, Xiaopu; Lu, Jiwei; Poon, Joseph; Comes, Ryan; Devaraj, Arun; Spurgeon, Steven
Amorphous ferrimagetic TbFeCo and TbSmFeCo thin films are found to exhibit strong perpendicular magnetic anisotropy. Self exchange bias effect and bi-stable magneto-resistance states are observed near compensation temperature by magnetic hysteresis loop, anomalous Hall effect and transverse magneto-resistance measurements. Atom probe tomography, scanning transmission electron microscopy, and energy dispersive spectroscopy mapping have revealed two nanoscale amorphous phases with different Tb concentration distributed within the amorphous films. The observed exchange anisotropy originates from the exchange interaction between the two nanoscale amorphous phases. Exchange bias effect is used for increasing stability in spin valves and magnetic tunneling junctions. This study opens up a new platform for using amorphous ferrimagnetic thin films that require no epitaxial growth in nanodevices.. The work was supported by the Defense Threat Reduction Agency Grant and the U.S. Department of Energy.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Raju, M.; Chaudhary, Sujeet; Pandya, D. K.
2013-08-07
Unconventional multi-jump magnetization reversal and significant in-plane uniaxial magnetic anisotropy (UMA) in the ion-beam sputtered amorphous Co{sub 20}Fe{sub 60}B{sub 20}(5–75 nm) thin films grown on Si/amorphous SiO{sub 2} are reported. While such multi-jump behavior is observed in CoFeB(10 nm) film when the magnetic field is applied at 10°–20° away from the easy-axis, the same is observed in CoFeB(12.5 nm) film when the magnetic field is 45°–55° away from easy-axis. Unlike the previous reports of multi-jump switching in epitaxial films, their observance in the present case of amorphous CoFeB is remarkable. This multi-jump switching is found to disappear when the filmsmore » are crystallized by annealing at 420 °C. The deposition geometry and the energy of the sputtered species appear to intrinsically induce a kind of bond orientation anisotropy in the films, which leads to the UMA in the as-grown amorphous CoFeB films. Exploitation of such multi-jump switching in amorphous CoFeB thin films could be of technological significance because of their applications in spintronic devices.« less
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Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition
NASA Astrophysics Data System (ADS)
Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty
2004-07-01
Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are derived from leaching of dust particles entrained in rain or fog droplets either in the atmosphere or during wet atmospheric deposition. The high trace metal enrichment factors require that most of the dust was physically removed before or during varnish formation. The remaining aqueous counterpart would be depleted in HFSEs and Th relative to the REEs, Co, Ni and Pb because the former are more insoluble and hence largely retained in the removed dust fraction. The high Ce/La ratios suggest that precipitation of trace metals may have been governed by equilibrium partitioning in an excess of wet atmospheric deposition. If varnishes are indeed derived from wet atmospheric deposition, they may provide a record of the aqueous component of atmospheric dust inputs to various environments.
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Wang, Ning; Xue, Xi-Mei; Juhasz, Albert L; Chang, Zhi-Zhou; Li, Hong-Bo
2017-01-01
Previous studies have shown that biochar enhances microbial reduction of iron (Fe) oxyhydroxide under anaerobic incubation. However, there is a lack of data on its influence on arsenic (As) release from As-contaminated paddy soils. In this study, paddy soil slurries (120 mg As kg -1 ) were incubated under anaerobic conditions for 60 days with and without the addition of biochar (3%, w/w) prepared from rice straw at 500 °C. Arsenic release, Fe reduction, and As fractionation were determined at 1, 10, 20, 30, and 60 d, while Illumina sequencing and real-time PCR were used to characterize changes in soil microbial community structure and As transformation function genes. During the first month of incubation, As released into soil solution increased sharply from 27.9 and 55.9 to 486 and 630 μg kg -1 in unamended and biochar amended slurries, with inorganic trivalent As (As III ) being the dominant specie (52.7-91.0% of total As). Compared to unamended slurries, biochar addition increased As and ferrous ion (Fe 2+ ) concentrations in soil solution but decreased soil As concentration in the amorphous Fe/Al oxide fraction (F3). Difference in released As between biochar and unamended treatments (ΔAs) increased with incubation time, showing strong linear relationships (R 2 = 0.23-0.33) with ΔFe 2+ and ΔF3, confirming increased As release due to enhanced Fe reduction. Biochar addition increased the abundance of Fe reducing bacteria such as Clostridum (27.3% vs. 22.7%), Bacillus (3.34% vs. 2.39%), and Caloramator (4.46% vs. 3.88%). In addition, copy numbers in biochar amended slurries of respiratory As reducing (arrA) and detoxifying reducing genes (arsC) increased 19.0 and 1.70 fold, suggesting microbial reduction of pentavalent As (As V ) adsorbed on Fe oxides to As III , further contributing to increased As release. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Enhanced Azo-Dyes Degradation Performance of Fe-Si-B-P Nanoporous Architecture
Weng, Nan; Wang, Feng; Qin, Fengxiang; Tang, Wanying; Dan, Zhenhua
2017-01-01
Nanoporous structures were fabricated from Fe76Si9B10P5 amorphous alloy annealed at 773 K by dealloying in 0.05 M H2SO4 solution, as a result of preferential dissolution of α-Fe grains in form of the micro-coupling cells between α-Fe and cathodic residual phases. Nanoporous Fe-Si-B-P powders exhibit much better degradation performance to methyl orange and direct blue azo dyes compared with gas-atomized Fe76Si9B10P5 amorphous powders and commercial Fe powders. The degradation reaction rate constants of nanoporous powders are almost one order higher than those of the amorphous counterpart powders and Fe powders, accompanying with lower activation energies of 19.5 and 26.8 kJ mol−1 for the degradation reactions of methyl orange and direct blue azo dyes, respectively. The large surface area of the nanoporous structure, and the existence of metalloids as well as residual amorphous phase with high catalytic activity are responsible for the enhanced azo-dyes degradation performance of the nanoporous Fe-Si-B-P powders. PMID:28846622
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The Samarco mine tailing disaster: A possible time-bomb for heavy metals contamination?
Queiroz, Hermano M; Nóbrega, Gabriel N; Ferreira, Tiago O; Almeida, Leandro S; Romero, Thais B; Santaella, Sandra T; Bernardino, Angelo F; Otero, Xosé L
2018-05-10
In November 2015, the largest socio-environmental disaster in the history of Brazil occurred when approximately 50 million m 3 of mine tailings were released into the Doce River (SE Brazil), during the greatest failure of a tailings dam worldwide. The mine tailings passed through the Doce River basin, reaching the ecologically important estuary 17 days later. On the arrival of the mine wastes to the coastal area, contamination levels in the estuarine soils were measured to determine the baseline level of contamination and to enable an environmental risk assessment. Soil and tailings samples were collected and analyzed to determine the redox potential (Eh), pH, grain size and mineralogical composition, total metal contents (Fe, Mn, Cr, Zn, Ni, Cu, Pb and Co) and organic matter content. The metals were fractionated to elucidate the mechanisms governing the trace metal dynamics. The mine tailings are mostly composed of Fe (mean values for Fe: 45,200 ± 2850; Mn: 433 ± 110; Cr: 63.9 ± 15.1; Zn: 62.4 ± 28.4; Ni: 24.7 ± 10.4; Cu: 21.3 ± 4.6; Pb: 20.2 ± 4.6 and Co: 10.7 ± 4.8 mg kg -1 ), consisting of Fe-oxyhydroxides (goethite, hematite); kaolinite and quartz. The metal contents of the estuarine soils, especially the surface layers, indicate trace metal enrichment caused by the tailings. However, the metal contents were below threshold levels reported in Brazilian environmental legislation. Despite the fact that only a small fraction (<2%) of the metals identified are readily bioavailable (i.e. soluble and exchangeable fraction), trace metals associated with Fe oxyhydroxides contributed between 69.8 and 87.6% of the total contents. Control of the trace metal dynamics by Fe oxyhydroxides can be ephemeral, especially in wetland soils in which the redox conditions oscillate widely. Indeed, the physicochemical conditions (Eh < 100 mV and circumneutral pH) of estuarine soils favor Fe reduction microbial pathways, which will probably increase the trace metal bioavailability and contamination risk. Copyright © 2018 Elsevier B.V. All rights reserved.
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Mechanism of Arsenic Adsorption Using Wheat Biomass -- a spectroscopic study
NASA Astrophysics Data System (ADS)
Calvo, Oscar; Manciu, Felicia; Maldonado, Josefina; Gardea-Torresdey, Jorge
2006-10-01
Arsenic is a trace element that is toxic to animals, humans included. Since the current Environmental Protection Agency guidelines regarding water quality standards indicate that arsenic concentrations in excess of 50 ppb are hazardous to welfare of humans, the search for new water remediation methods or improvements of previous methods have been a focus in environmental technology. Investigations of arsenic uptake have used wide range of sorbents including iron oxides and oxyhydroxides, for which it have been proved that arsenic shows high affinity. In this study, we used far-infrared spectroscopy to examine the arsenic reduction using biomaterials. pH dependence analysis by FTIR demonstrates the sorption of iron oxides and oxyhydroxides by the wheat biomass. The splitting of 350 cm-1 amorphous iron oxide vibrations is a direct proof of the arsenic uptake. In addition, there is evidence of sorption of arsenic at sulfhydryl group of cysteine existent in wheat.
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Electrical and Magnetic Properties of Binary Amorphous Transition Metal Alloys.
NASA Astrophysics Data System (ADS)
Liou, Sy-Hwang
The electrical, superconductive and magnetic properties of several binary transition metal amorphous and metastable crystalline alloys, Fe(,x)Ti(,100-x) (30 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Zr(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 93), Fe(,x)Hf(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 100), Fe(,x)Nb(,100 -x) (22 (LESSTHEQ) x (LESSTHEQ) 85), Ni(,x)Nb(,100-x) (20 (LESSTHEQ) x (LESSTHEQ) 80), Cu(,x)Nb(,100-x) (10 (LESSTHEQ) x (LESSTHEQ) 90) were studied over a wide composition range. Films were made using a magnetron sputtering system, and the structure of the films was investigated by energy dispersive x-ray diffraction. The composition region of each amorphous alloys system was determined and found in good agreement with a model proposed by Egami and Waseda. The magnetic properties and hyperfine interactions in the films were investigated using a conventional Mossbauer spectrometer and a ('57)Co in Rh matrix source. In all Fe-early transition metal binary alloys systems, Fe does not retain its moment in the low iron concentration region and the result is that the critical concentration for magnetic order (x(,c)) is much larger than anticipated from percolation considerations. A direct comparison between crystalline alloys and their amorphous counterparts of the same composition illustrate no clear correlation between crystalline and amorphous states. Pronounced discontinuities in the magnetic properties with variation in Fe content of all Fe-early transition metal alloys at phase boundaries separating amorphous and crystalline states have been observed. This is caused by the differences in the atomic arrangement and the electronic structure between crystalline and amorphous solids. The temperature dependence of resistivity, (rho)(T), of several binary amorphous alloys of Fe-TM (where TM = Ti, Zr, Hf, Nb etc.) has been studied from 2K to 300K. The Fe-poor (x < x(,c)) samples and the Fe-rich (x > x(,c)) samples have distinctive differences in (rho)(T) at low temperature (below 30K). All the magnetic samples show a logarithmic dependence at low temperature that can be described by Kondo scattering. In addition, there is a change in slope of (rho)(T) at a temperature close to the magnetic ordering temperature, indicating a contribution attributed to magnetic ordering. Several Nb-based amorphous alloys (Fe-Nb, Ni-Nb, Cu-Nb) have also been systematically studied. The effect of the magnetic species on superconductivity is investigated. The value of superconducting transition temperature (T(,s)) increases linearly with increasing Nb concentration. (Abstract shortened with permission of author.).
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NASA Astrophysics Data System (ADS)
Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas
2015-09-01
Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic ligands (e.g., SiO44- or PO43-), may form in many natural Fe(II)-oxidizing environments. We propose that the formation of these intermediates is likely to occur in organic-rich systems, and thus may have controlled the ultimate isotopic composition of Fe minerals in systems where Fe(II) was being oxidized by or in the presence of microbes in Earth's past.
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NASA Astrophysics Data System (ADS)
Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.
2008-04-01
This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.
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Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J
2016-01-01
Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.
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Influence of iron redox cycling on organo-mineral associations in arctic tundra soils
NASA Astrophysics Data System (ADS)
Herndon, E.; AlBashaireh, A.; Duroe, K.; Singer, D. M.
2016-12-01
Geochemical interactions between soil organic matter and minerals influence decomposition in many environments but remain poorly understood in arctic tundra systems. In tundra soils that are periodically to persistently saturated, the accumulation of iron oxyhydroxides and organo-iron precipitates at redox interfaces may inhibit decomposition by binding organic molecules and protecting them from microbial degradation. Here, we couple synchrotron-source spectroscopic techniques with chemical sequential extractions and physical density fractionations to evaluate the spatial distribution and speciation of Fe-bearing phases and associated organic matter in organic and mineral horizons of the seasonally thawed active layer in tundra soils from northern Alaska. Mineral-associated organic matter comprised 63 ± 9% of soil organic carbon stored in the active layer of ice wedge polygons. Ferrous iron produced in anoxic mineral horizons diffused upwards and precipitated as poorly-crystalline oxyhydroxides and organic-bound Fe(III) in the organic horizons. Ferrihydrite and goethite were present as coatings on mineral grains and plant debris and in aggregates with clays and particulate organic matter. Organic matter released through acid-dissolution of iron oxides may represent a small pool of readily-degradable organic molecules temporarily stabilized by sorption to iron oxyhydroxide surfaces, while larger quantities of particulate organic carbon and humic-like substances may be physically protected from decomposition by Fe-oxide coatings and aggregation. We conclude that formation of poorly-crystalline and crystalline iron oxides at redox interfaces contributes to mineral protection of organic matter through sorption, aggregation, and co-precipitation reactions. Further study of organo-mineral associations is necessary to determine the net impact of mineral-stabilization on carbon storage in rapidly warming arctic ecosystems.
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The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water
NASA Astrophysics Data System (ADS)
Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.
2014-12-01
Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.
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Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes
NASA Astrophysics Data System (ADS)
Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.
2017-04-01
Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.
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NASA Astrophysics Data System (ADS)
Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick
2015-02-01
The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD < 5 kDa). The Fe isotopic composition and electron paramagnetic resonance (EPR) species were measured on these different pore-sized fractions. The acidic and organo-Fe-rich waters of the Negro River displayed dissolved and colloidal fractions enriched in heavy isotopes (∼1.2‰, in δ57Fe values relative to IRMM-14), while the particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic composition of colloidal and dissolved Fe from the Negro River are consistent with Fe oxidation and complexation mechanisms at the interface between waterlogged podzols and river networks, as supported by strong organo-Fe complexes signals observed by EPR. Conversely, the particulate and colloidal fractions from the Solimões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.
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Sequestration of non-pure carbon dioxide streams in iron oxyhydroxide-containing saline repositories
Garcia, S.; Rosenbauer, Robert J.; Palandri, James L.; Maroto-Valer, M. Mercedes
2012-01-01
Iron oxyhydroxide, goethite (α-FeOOH), was evaluated as a potential formation mineral reactant for trapping CO2 in a mineral phase such as siderite (FeCO3), when a mixture of CO2-SO 2 flue gas is injected into a saline aquifer. Two thermodynamic simulations were conducted, equilibrating a CO2-SO2 fluid mixture with a NaCl-brine and Fe-rich rocks at 150 °C and 300 bar. The modeling studies evaluated mineral and fluid composition at equilibrium and the influence of pH buffering in the system. Results show siderite precipitates both in the buffered and unbuffered system; however, the presence of an alkaline pH buffer enhances the stability of the carbonate. Based on the model, an experiment was designed to compare with thermodynamic predictions. A CO2-SO2 gas mixture was reacted in 150 ml of NaCl-NaOH brine containing 10 g of goethite at 150 °C and 300 bar for 24 days. Mineralogical and brine chemistry confirmed siderite as the predominant reaction product in the system. Seventy-six mg of CO2 are sequestered in siderite per 10 g of goethite.
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NASA Astrophysics Data System (ADS)
Jones, Catherine L.; Brearley, Adrian J.
2006-02-01
We have performed an experimental study of the aqueous alteration of the Allende CV3 carbonaceous chondrite under highly oxidizing conditions, in order to examine the alteration behavior of Allende's anhydrous mineralogy. The experiments were carried out at temperatures of 100, 150, and 200 °C, for time periods between 7 and 180 days, with water/rock ratios ranging from 1:1 to 9:1. Uncrushed cubes of Allende were used so that the spatial relationships between reactant and product phases could be examined in detail. Scanning electron microscope studies show that in all the experiments, even those of short duration (7 days), soluble salts of Ca and Mg (CaSO 4, CaCO 3, and MgSO 4) precipitated on the sample surface, indicating that these elements are rapidly mobilized during alteration. In addition, iron oxides and hydroxides formed on the sample surfaces. The sulfates, carbonates, and the majority of the iron-bearing secondary minerals are randomly distributed over the surface of samples. In some instances the iron oxides and hydroxides are constrained to the boundaries of altering mineral grains. Transmission electron microscope studies show that the FeO-rich olivine in the interior of the samples has altered to form interlayered serpentine/saponite and Fe-oxyhydroxides. The degree of alteration increases significantly with increasing water/rock ratio, and to a lesser extent with increasing duration of heating. The serpentine/saponite forms both by direct replacement of the olivine in crystallographically oriented intergrowths, and by recrystallization of an amorphous Si-rich phase that precipitates in pore space between the olivine grains. The alteration assemblage bears many similarities to those found in altered carbonaceous chondrites, although in detail there are important differences, which we attribute to (a) the relatively high temperatures of our experiments and (b) comparatively short reaction times compared with the natural examples. In terms of mineral assemblage, our experiments most closely resemble alteration in the CI chondrites, although the degree of alteration of our experiments is much lower. CI chondrites contain serpentine/saponite intergrowths and veins of Ca-sulfate and Ca-carbonate as well as the Fe-oxyhydroxide, ferrihydrite. However, the phyllosilicate phases formed in our experiments are somewhat coarser-grained than the finest phyllosilicate fraction present in CI chondrites, suggesting that alteration of the CI chondrites occurred at lower temperatures. In terms of mineral assemblage, our experiments also appear to come close to matching CR chondrites, although we infer that CR alteration probably occurred at temperatures <100 °C, based on the very fine-grained size of phyllosilicates in CR matrices.
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Fu, Chaoqun; Xu, Lijun; Dan, Zhenhua; Makino, Akihiro; Hara, Nobuyoshi; Qin, Fengxiang; Chang, Hui
2017-01-01
Nanoporous electrodes have been fabricated by selectively dissolving the less noble α-Fe crystalline phase from nanocrystalline Fe85.2B14–xPxCu0.8 alloys (x= 0, 2, 4 at.%). The preferential dissolution is triggered by the weaker electrochemical stability of α-Fe nanocrystals than amorphous phase. The final nanoporous structure is mainly composed of amorphous residual phase and minor undissolved α-Fe crystals and can be predicted from initial microstructure of nanocrystalline precursor alloys. The structural inheritance is proved by the similarity of the size and outlines between nanopores formed after dealloying in 0.1 M H2SO4 and α-Fe nanocrystals precipitated after annealing of amorphous Fe85.2B14−xPxCu0.8 (x = 0, 2, 4 at.%) alloys. The Redox peak current density of the nanoporous electrodes obtained from nanocrystalline Fe85.2B10P4Cu0.8 alloys is more than one order higher than those of Fe plate electrode and its counterpart nanocrystalline alloys due to the large surface area and nearly-amorphous nature of ligaments. PMID:28594378
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.
Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less
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Grenne, Tor; Slack, John F.
2005-01-01
Stratiform beds of jasper (hematitic chert), composed essentially of SiO2 (69-95 wt %) and Fe2O3 (3-25 wt %), can be traced several kilometers along strike in the Ordovician L??kken ophiolite, Norway. These siliceous beds are closely associated with volcanogenic massive sulfide (VMS) deposits and are interpreted as sea-floor gels that were deposited by fallout from hydrothermal plumes in silica-rich seawater, in which plume-derived Fe oxyhydroxide particles promoted flocculation and rapid settling of large (???200 ??m) colloidal particles of silica-iron oxyhydroxide. Concentrations of chalcophile elements in the jasper beds are at the parts per million level implying that sulfide particle fallout was insignificant and that the Si-Fe gel-forming plumes were mainly derived from intermediate- (100??-250??C) to high-temperature (>250??) white smoker-type vents with high Fe/S ratios. The interpreted setting is similar to that of the Lau basin, where high-temperature (280??-334??C) white smoker venting alternates or overlaps with sulfide mound-forming black smoker venting. Ratios of Al, Sc, Th, Hf, and REE to iron are very low and show that the detrital input was <0.1 percent of the bulk jasper. Most jasper beds are enriched in U, V, P, and Mo relative to the North American Shale Composite, reflecting a predominantly seawater source, whereas REE distribution patterns (positive Eu and negative Ce anomalies) reflect variable mixing of hydrothermal solutions with oxic seawater at dilution ratios of ???102 to 104. Trace element variations in the gel precursor to the jasper are thought to have been controlled by coprecipitation and/or adsorption by Fe oxyhydroxide particles that formed by the oxidation of hydrothermal Fe2+ within the variably seawater-diluted hydrothermal plume(s). Thick jasper layers near the H??ydal VMS orebody show distinct positive As/Fe and Sb/Fe anomalies that are attributed to near-vent rapid settling of Si-Fe particles derived from As- and Sb-rich hydrothermal fluids prior to extensive mixing with seawater in the buoyant plume. Particles that formed later in the highly diluted nonbuoyant plume formed relatively As and Sb poor distal jasper. The large particle sizes and accordingly high settling rates of the particles, together with mass-balance calculations based on modern vent field data, suggest that individual meter-thick jasper beds formed within a plume lifetime of 200 years or less. The lack of thick jasper beds near the L??kken VMS orebody, which is larger than the H??ydal orebody by more than two orders of magnitude, probably reflects a shift to anoxic conditions during L??kken mineralization. This environment limited oxidation of iron in the hydrothermal plume and formation of the ferric oxyhydroxides necessary for the flocculation of silica and sea-floor deposition of the gel precursor of the jasper beds. Distal pyritic and iron-poor cherts are more common than jasper in ancient VMS-hosting sequences. The origin of these other types of siliceous exhalite is enigmatic but at least in some cases involved sulfidation, reduction to magnetite, or dissolution of the original ferric iron in precursor Si-rich gels, either by hydrothermal or diagenetic processes. ?? 2005 Society of Economic Geologists, Inc.
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Evaluation of different amendments to stabilize antimony in mining polluted soils.
Álvarez-Ayuso, E; Otones, V; Murciego, A; García-Sánchez, A
2013-02-01
Soil pollution with antimony is of increasing environmental concern worldwide. Measures for its control and to attenuate the risks posed to the ecosystem are required. In this study the application of several iron and aluminium oxides and oxyhydroxides as soil amendments was evaluated in order to assess their feasibility to stabilize Sb in mining polluted soils. Mine soils with different pollution levels were amended with either goethite, ferrihydrite or amorphous Al oxide at various ratios (0-10%). The effectiveness of such treatments was assessed by both batch and column leaching tests. The use of ferrihydrite or amorphous Al oxide proved to be highly effective to stabilize Sb. Immobilization levels of 100% were found when doses of 5% ferrihydrite or 10% amorphous Al oxide were applied, regardless of the soil Sb load. Column leaching studies also showed a high Sb leaching reduction (>75%) when soils were amended with 1% ferrihydrite or 5% amorphous Al oxide. Moreover, such treatments proved to simultaneously immobilize As and Pb in a great extent when soils were also polluted with such toxic elements. Copyright © 2012 Elsevier Ltd. All rights reserved.
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Shikazono, N; Tatewaki, K; Mohiuddin, K M; Nakano, T; Zakir, H M
2012-01-01
Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.
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NASA Astrophysics Data System (ADS)
Cao, C. C.; Zhu, L.; Meng, Y.; Zhai, X. B.; Wang, Y. G.
2018-06-01
The evolution of local structure and defects in the Fe81Si4B10P4Cu1 amorphous alloy during the structural relaxation has been investigated by Mössbauer spectroscopy, positron annihilation lifetime spectroscopy and transmission electron microscopy to explore their effects on magnetic properties of the nanocrystalline. The atomic rearrangements at the early stage of the structural relaxation cause the density increase of the amorphous matrix, but the subsequent atomic rearrangements contribute to the transformation of Fe3B-like atomic arrangements to FeB-like ones with the temperature increasing. As the structural relaxation processes, the released Fe atoms both from Fe3B- and Fe3P-like atomic arrangements result in the formation of new Fe clusters and the increase of Fe-Fe coordination number in the existing Fe clusters and the nucleation sites for α-Fe gradually increase, both of which promote the crystallization. However, the homogeneity of amorphous matrix will be finally destroyed under excessive relaxation temperature, which coarsens nanograins during the crystallization instead. Therefore, soft magnetic properties of the Fe81Si4B10P4Cu1 nanocrystalline alloy can be improved by pre-annealing the amorphous precursor at an appropriate temperature due to the atomic level structural optimization.
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Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.
Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M
2012-12-01
Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.
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Potter-McIntyre, Sally L; Chan, Marjorie A; McPherson, Brian J
2014-01-01
Iron (oxyhydr)oxide microbial mats in modern to ∼100 ka tufa terraces are present in a cold spring system along Ten Mile Graben, southeastern Utah, USA. Mats exhibit morphological, chemical, and textural biosignatures and show diagenetic changes that occur over millennial scales. The Jurassic Brushy Basin Member of the Morrison Formation in the Four Corners region of the USA also exhibits comparable microbial fossils and iron (oxyhydr)oxide biosignatures in the lacustrine unit. Both the modern spring system and Brushy Basin Member represent alkaline, saline, groundwater-fed systems and preserve diatoms and other similar algal forms with cellular elaboration. Two distinct suites of elements (1. C, Fe, As and 2. C, S, Se, P) are associated with microbial fossils in modern and ancient iron (oxyhydr)oxides and may be potential markers for biosignatures. The presence of ferrihydrite in ∼100 ka fossil microbial mats and Jurassic rocks suggests that this thermodynamically unstable mineral may also be a potential biomarker. One of the most extensive sedimentary records on Mars is exposed in Gale Crater and consists of non-acidic clays and sulfates possibly of lacustrine origin. These terrestrial iron (oxyhydr)oxide examples are a valuable analogue because of similar iron- and clay-rich host rock compositions and will help (1) understand diagenetic processes in a non-acidic, saline lacustrine environment such as the sedimentary rocks in Gale Crater, (2) document specific biomediated textures, (3) demonstrate how biomediated textures might persist or respond to diagenesis over time, and (4) provide a ground truth library of textures to explore and compare in extraterrestrial iron (oxyhydr)oxides, where future explorations hope to detect past evidence of life.
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Wang, Xiao; Luo, Yapeng; Huang, Tao; Liu, Huixia
2017-01-01
Recently, amorphous alloys have attracted many researchers’ attention for amorphous structures and excellent properties. However, the welding of amorphous alloys to traditional metals in the microscale is not easy to realize in the process with amorphous structures unchanged, which restrains the application in industry. In this paper, a new method of welding Fe-based amorphous alloys (GB1K101) to crystalline copper by laser impact welding (LIW) is investigated. A series of experiments was conducted under different laser energies, during which Fe-based amorphous alloys and crystalline copper were welded successfully by LIW. In addition, the microstructure and mechanical properties of welding joints were observed and measured, respectively. The results showed that the surface wave and springback were observed on the flyer plate after LIW. The welding interface was straight or wavy due to different plastic deformation under different laser energies. The welding interface was directly bonded tightly without visible defects. No visible element diffusion and intermetallic phases were found in the welding interface. The Fe-based amorphous alloys retained amorphous structures after LIW under the laser energy of 835 mJ. The nanoindentation hardness across the welding interface showed an increase on both sides of the welding interface. The results of the lap shearing test showed that the fracture position was on the side of copper coil. PMID:28772886
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Wang, Xiao; Luo, Yapeng; Huang, Tao; Liu, Huixia
2017-05-12
Recently, amorphous alloys have attracted many researchers' attention for amorphous structures and excellent properties. However, the welding of amorphous alloys to traditional metals in the microscale is not easy to realize in the process with amorphous structures unchanged, which restrains the application in industry. In this paper, a new method of welding Fe-based amorphous alloys (GB1K101) to crystalline copper by laser impact welding (LIW) is investigated. A series of experiments was conducted under different laser energies, during which Fe-based amorphous alloys and crystalline copper were welded successfully by LIW. In addition, the microstructure and mechanical properties of welding joints were observed and measured, respectively. The results showed that the surface wave and springback were observed on the flyer plate after LIW. The welding interface was straight or wavy due to different plastic deformation under different laser energies. The welding interface was directly bonded tightly without visible defects. No visible element diffusion and intermetallic phases were found in the welding interface. The Fe-based amorphous alloys retained amorphous structures after LIW under the laser energy of 835 mJ. The nanoindentation hardness across the welding interface showed an increase on both sides of the welding interface. The results of the lap shearing test showed that the fracture position was on the side of copper coil.
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Novel Amorphous Fe-Zr-Si(Cu) Boron-free Alloys
NASA Astrophysics Data System (ADS)
Kopcewicz, M.; Grabias, A.; Latuch, J.; Kowalczyk, M.
2010-07-01
Novel amorphous Fe80(ZrxSi20-x-y)Cuy boron-free alloys, in which boron was completely replaced by silicon as a glass forming element, have been prepared in the form of ribbons by a melt quenching technique. The X-ray diffraction and Mössbauer spectroscopy measurements revealed that the as-quenched ribbons with the composition of x = 6-10 at. % and y = 0, 1 at. % are predominantly amorphous. DSC measurements allowed the estimation of the crystallization temperatures of the amorphous alloys. The soft magnetic properties have been studied by the specialized rf-Mössbauer technique in which the spectra were recorded during an exposure of the samples to the rf field of 0 to 20 Oe at 61.8 MHz. Since the rf-collapse effect observed is very sensitive to the local anisotropy fields it was possible to evaluate the soft magnetic properties of amorphous alloys studied. The rf-Mössbauer studies were accompanied by the conventional measurements of the quasi-static hysteresis loops from which the magnetization and coercive fields were estimated. It was found that amorphous Fe-Zr-Si(Cu) alloys are magnetically very soft, comparable with those of the conventional amorphous B-containing Fe-based alloys.
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NASA Astrophysics Data System (ADS)
van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.
2014-06-01
The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
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NASA Astrophysics Data System (ADS)
van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.
2014-11-01
The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.
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Migration of 75Se(IV) in crushed Beishan granite: Effects of the iron content.
He, Jiangang; Ma, Bin; Kang, Mingliang; Wang, Chunli; Nie, Zhe; Liu, Chunli
2017-02-15
The diffusion of selenite (labeled with 75 Se) in compacted Beishan granite (BsG) was investigated using the in-diffusion capillary method at pH values from ∼2.0 to ∼11.0 under oxic and anoxic conditions. The results indicate that the apparent diffusion coefficient (D a ) values of selenite in BsG always reached the minimum at approximately pH 5. Unexpectedly, the D a values under oxic conditions are nearly one order of magnitude lower than those under the anoxic conditions. Further characterization reveals the existence of redox-sensitive Fe(II)-containing components, which can be responsible for the great difference in D a values. Fe(2p) X-ray photoelectron spectroscopy (XPS) results show that more Fe(III)-oxyhydroxide coating is formed on the granite's surface under aerobic conditions than is formed under anaerobic conditions. Correspondingly, Se(3d) spectra indicate that more selenium is sorbed under oxic conditions, and the sorbed amount always reached the maximum at pH values from ∼4 to ∼5. A linear combination fit of X-ray absorption near edge structure (XANES) spectroscopy data revealed that Se(0) was formed under anoxic condition and that selenite preferred to form inner-sphere complexes with Fe(III)-oxyhydroxide. Overall, this study indicates that natural Fe-bearing minerals can greatly attenuate selenite diffusion and the retardation would be enhanced under aerobic conditions. Copyright © 2016 Elsevier B.V. All rights reserved.
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The nanosphere iron mineral(s) in Mars soil
NASA Technical Reports Server (NTRS)
Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.
1993-01-01
A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.
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Generalized Slater--Pauling curve and the role of metalloids in Fe-based amorphous alloys
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sostarich, M.
1990-05-01
A modification of the generalized Slater--Pauling curve so as to consider the concentration dependence of the number of majority-spin {ital sp} electrons per average atom is proposed for amorphous iron-metalloid alloys. In this way an improved matching of the measured magnetic moment dependence on composition is achieved for Fe alloys with B and/or P as metalloids. Comparison of theory with experiment shows that amorphous Fe-P alloys tend to be magnetically rather strong, whereas their Fe-B counterparts are weak itinerant ferromagnets in almost the entire range of compositions.
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P-V-T equation of state of rhodium oxyhydroxide
NASA Astrophysics Data System (ADS)
Suzuki, Akio
2018-04-01
A high pressure X-ray diffraction study of RhOOH was carried out up to 17.44 GPa to investigate the compression behavior of an oxyhydroxide with an InOOH-related structure. A fit to the third-order Birch-Murnaghan equation of state gave K0 = 208 ± 6 GPa, and K‧ = 9.4 ± 1.3. The temperature derivative of the bulk modulus was found to be ∂K/∂T = -0.06 ± 0.02 GPa K-1. The refined parameters for volume thermal expansion were α0 = 2.7 ± 0.3 × 10-5 K-1; α1 = 1.7 ± 1.1 × 10-8 K-2 in the polynomial form (α(T) = α0 + α1(T-300)). Our results show that RhOOH is very incompressible, and has a higher bulk modulus than other InOOH-structured oxyhydroxides (e.g. δ-AlOOH, ε-FeOOH, and γ-MnOOH).
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Fluxing purification and its effect on magnetic properties of high-Bs FeBPSiC amorphous alloy
NASA Astrophysics Data System (ADS)
Pang, Jing; Wang, Anding; Yue, Shiqiang; Kong, Fengyu; Qiu, Keqiang; Chang, Chuntao; Wang, Xinmin; Liu, Chain-Tsuan
2017-07-01
A high-Bs amorphous alloy with the base composition Fe83B11P3Si2C1 was used to study the effects of fluxing purification on amorphous forming ability and magnetic properties of the alloy prepared with raw materials in industrialization. By using fluxing purification, the surface crystallization was suppressed and fully amorphous Fe83B11P3Si2C1 ribbons with a maximum thickness of 48 μm were successfully achieved by using an industrial process and materials. The amorphous ribbons made with industrial-purified alloys exhibit excellent magnetic properties, containing high-Bs of 1.65 T, low Hc of 2.0 A/m, and high μe of 9.7 × 103 at 1 kHz. Impurities in the melting alloys exist in three forms and have different effluences on magnetic properties. The surface crystallization was triggered by the impurities which exist as high melting point inclusions serving as nuclei. Thus, fluxing purification is a feasible way for industrialization of high-Bs FeBPSiC amorphous alloys.
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Thermal reaction of sonochemically prepared amorphous Fe/C
NASA Astrophysics Data System (ADS)
Miyatani, R.; Kobayashi, Y.; Yamada, Y.
2017-11-01
An amorphous iron/carbon mixture was prepared by sonolysis of ferrocene in diphenylmethane. Heating of the amorphous mixture at 900 or 1200 °C produced nanoparticles, which were then analyzed using Mössbauer spectroscopy, X-ray diffraction, and transmission electron microscopy. The nanoparticles obtained after heating were spherical with diameters of about 50 nm. The sample obtained after heating at 900 °C consisted of α-Fe and Fe 3C, whereas the sample obtained after heating at 1200 °C consisted of α-Fe and γ-Fe. The reaction of the mixture during the heating process was accompanied by the formation of carbon nanotubes catalyzed by the iron or iron carbide nanoparticles.
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NASA Astrophysics Data System (ADS)
Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.
1996-04-01
The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.
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Xiao, Wei; Jones, Adele M; Collins, Richard N; Waite, T David
2018-05-09
The inorganic core of the iron storage protein, ferritin, is recognized as being analogous to the poorly crystalline iron mineral, ferrihydrite (Fh). Fh is also abundant in soils where it is central to the redox cycling of particular soil contaminants and trace elements. In geochemical circles, it is recognized that Fh can undergo Fe(II)-catalyzed transformation to form more crystalline iron minerals, vastly altering the reactivity of the iron oxide and, in some cases, the redox poise of the system. Of relevance to both geochemical and biological systems, we investigate here if the naturally occurring reducing agent, ascorbate, can effect such an Fe(II)-catalyzed transformation of Fh at 25 °C and circumneutral pH. The transformation of ferrihydrite to possible secondary Fe(III) mineralization products was quantified using Fourier transform infrared (FTIR) spectroscopy, with supporting data obtained using X-ray absorbance spectroscopy (XAS) and X-ray diffraction (XRD). Whilst the amount of Fe(II) formed in the presence of ascorbate has resulted in Fh transformation in previous studies, no transformation of Fh to more crystalline Fe(III) (oxyhydr)oxides was observed in this study. Further experiments indicated this was due to the ability of ascorbate to inhibit the formation of goethite, lepidocrocite and magnetite. The manner in which ascorbate associated with Fh was investigated using FTIR and total organic carbon (TOC) analysis. The majority of ascorbate was found to adsorb to the Fh surface under anoxic conditions but, under oxic conditions, ascorbate was initially adsorbed then became incorporated within the Fe(III) (oxyhydr)oxide structure (i.e., co-precipitated) over time. Copyright © 2018 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Matsukage, K. N.; Nishihara, Y.
2015-12-01
We experimentally discovered a new hydrous phase in the system FeOOH-TiO2 at pressures of 10-16 GPa and temperatures of 1000-1600°C which corresponds to conditions of the deep upper mantle and the Earth's mantle transition zone. Seven different compositions in the FeOOH-TiO2 system having molar ratios of x = Ti/(Fe + Ti) = 0, 0.125, 0.25, 0.375, 0.5, 0.75 that were prepared by mixing reagent grade a-FeOOH (goethite) and TiO2 (anatase) powders were used as starting materials. High-pressure and high-temperature experiments were carried out using Kawai-type multi-anvil apparatus (Orange-1000 at Ehime University and SPI-1000 at Tokyo Institute of Technology). In this system, we identified two stable iron-titanium oxyhydroxide phases whose estimated composition is expressed by (FeH)1 - xTixO2 . One is the Fe-rich solid solution (x < 0.23) with e-FeOOH type crystal structure (e-phase, orthorhombic, P21nm) that was described by the previous studies (e.g., Suzuki 2010), and the other is the more Ti-rich solid solution (x > 0.35) with a-PbO2 type structure (a-phase, orthorhombic, Pbcn). The a-phase is stable up to 1500ºC for a composition of x = 0.5 and at least to 1600ºC for x = 0.75. Our result means that this phase is stable at average mantle temperature in the Earth's mantle transition zone. The Iron-titanium-rich hydrous phases was possible to stable in basalt + H2O system (e.g., Hashimoto and Matsukage 2013). Therefore our findings suggest that water transport in the Earth's deep interior is probably much more efficient than had been previously thought.
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Galvanic Corrosion of Lead by Iron (Oxyhydr)Oxides: Potential Impacts on Drinking Water Quality.
Trueman, Benjamin F; Sweet, Gregory A; Harding, Matthew D; Estabrook, Hayden; Bishop, D Paul; Gagnon, Graham A
2017-06-20
Lead exposure via drinking water remains a significant public health risk; this study explored the potential effects of upstream iron corrosion on lead mobility in water distribution systems. Specifically, galvanic corrosion of lead by iron (oxyhydr)oxides was investigated. Coupling an iron mineral cathode with metallic lead in a galvanic cell increased lead release by 531 μg L -1 on average-a 9-fold increase over uniform corrosion in the absence of iron. Cathodes were composed of spark plasma sintered Fe 3 O 4 or α-Fe 2 O 3 or field-extracted Fe 3 O 4 and α-FeOOH. Orthophosphate immobilized oxidized lead as insoluble hydroxypyromorphite, while humic acid enhanced lead mobility. Addition of a humic isolate increased lead release due to uniform corrosion by 81 μg L -1 and-upon coupling lead to a mineral cathode-release due to galvanic corrosion by 990 μg L -1 . Elevated lead in the presence of humic acid appeared to be driven by complexation, with 208 Pb and UV 254 size-exclusion chromatograms exhibiting strong correlation under these conditions (R 2 average = 0.87). A significant iron corrosion effect was consistent with field data: lead levels after lead service line replacement were greater by factors of 2.3-4.7 at sites supplied by unlined cast iron distribution mains compared with the alternative, lined ductile iron.
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Data from the Mars Science Laboratory CheMin XRD/XRF Instrument
NASA Technical Reports Server (NTRS)
Vaniman, David; Blake, David; Bristow, Tom; DesMarais, David; Achilles, Cherie; Anderson, Robert; Crips, Joy; Morookian, John Michael; Spanovich, Nicole; Vasavada, Ashwin;
2013-01-01
The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity uses a Co tube source and a CCD detector to acquire mineralogy from diffracted primary X-rays and chemical information from fluoresced X-rays. CheMin has been operating at the MSL Gale Crater field site since August 5, 2012 and has provided the first X-ray diffraction (XRD) analyses in situ on a body beyond Earth. Data from the first sample collected, the Rocknest eolian soil, identify a basaltic mineral suite, predominantly plagioclase (approx.An50), forsteritic olivine (approx.Fo58), augite and pigeonite, consistent with expectation that detrital grains on Mars would reflect widespread basaltic sources. Minor phases (each <2 wt% of the crystalline component) include sanidine, magnetite, quartz, anhydrite, hematite and ilmenite. Significantly, about a third of the sample is amorphous or poorly ordered in XRD. This amorphous component is attested to by a broad rise in background centered at approx.27deg 2(theta) (Co K(alpha)) and may include volcanic glass, impact glass, and poorly crystalline phases including iron oxyhydroxides; a rise at lower 2(theta) may indicate allophane or hisingerite. Constraints from phase chemistry of the crystalline components, compared with a Rocknest bulk composition from the APXS instrument on Curiosity, indicate that in sum the amorphous or poorly crystalline components are relatively Si, Al, Mg-poor and enriched in Ti, Cr, Fe, K, P, S, and Cl. All of the identified crystalline phases are volatile-free; H2O, SO2 and CO2 volatile releases from a split of this sample analyzed by the SAM instrument on Curiosity are associated with the amorphous or poorly ordered materials. The Rocknest eolian soil may be a mixture of local detritus, mostly crystalline, with a regional or global set of dominantly amorphous or poorly ordered components. The Rocknest sample was targeted by MSL for "first time analysis" to demonstrate that a loose deposit could be scooped, sieved to <150 microns, and delivered to instruments in the body of the rover. A drilled sample of sediment in outcrop is anticipated. At the time of writing this abstract, promising outcrops are in range and this talk will provide an update on data collected with the CheMin instrument.
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NASA Astrophysics Data System (ADS)
Otero, Xosé Luis; Pérez-Alberti, Augusto; Gónzalez, Adrián; Macias, Felipe
2013-04-01
The study area, Mount Martial, is located in the South of Argentina, in the Tierra de Fuego province (54°S, 68°W). The climate in Tierra del Fuego is temperate-cold and humid, with a strong and markedly seasonal oceanic influence. The mean air temperature that we recorded in the study zone, at 1050 m above sea level, between February 2005 and January 2010 was -1.9° C, with an absolute maximum of 12.5° C and an absolute minimum of -12.8° C. Although we have no rainfall data, in Ushuaia, which is close to sea level, the mean annual rainfall for 1961-1970 was 550 mm; however, it would be inaccurate to extrapolate this value given the marked variability in precipitation favoured by the relief. Biogeographically, the area is included in the so-called "Andean Desert", which is almost barren of large plants and with poor vegetable cover. At 800 a.s.l., the vegetation consists of shrubs of specialised taxons such as Bolax gummifera, Moschopsis rosulata and Saxifraga magellanica. In the present study, samples of Bolax gummifera rhizosphere (Umbelliferae), bulk soil and subsurface soils (>5 cm to rock layer) were collected from a small homogeneous area (≈500m2). The soils were characterized by analysis of pH (H2O and KCl), electrical conductivity, total organic carbon, total nitrogen, organic carbon, iron extracted with sodium pyrophosphate, and particle size. Sequential extraction of Fe in the samples was also carried out to determine the following fractions: F1: exchangeable fraction (extracted with 1M MgCl2), F2: amorphous Fe oxyhydroxides (extracted with sodium ascorbate-citrate buffering to pH 8 with sodium bicarbonate), F3: crystalline Fe oxyhydroxides (extracted with 0.11 sodium citrate+ sodium bicarbonate +3 g of sodium dithionite), and F4: organic Fe (extracted with 0.02M HNO3+30%H2O2 at 85°C) and bioavailability nutrients (soluble in Mehlich 3 extratant). The results obtained for the basic physicochemical characteristics of the soils revealed some differences between samples. Thus, Although these are poorly developed soils, significant differences were foundAlthough being incipient soils, significant differences were found in relation to the effect of the rhizosphere on soil properties. For example, the total organic C was 8 times higher and the total nitrogen and C pyrophosphate were 4 times higher in the rhizosphere than in the bulk soil. The results of the sequential extraction of Fe and bioavailability nutrients, such Ca, Mg, K and Fe, also revealed significant differences between rhizosphere and bulk soil, whereas the deeper samples (> 5 cm) displayed intermediate characteristics. These results are consistent with the hypothesis that plants affect the biogeochemical processes in soils by accelerating weathering processes. This aspect may be of particular importance within the context of global climate change, as higher temperatures will favour expansion of vegetation and at the same time the flow of nutrients towards oceans and lakes, which may have a direct effect on primary productivity.
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Synchronized Re-Entrant Flux Reversal of Multiple FeSiB Amorphous Wires Having the Larger Output
NASA Astrophysics Data System (ADS)
Takajo, Minoru; Yamasaki, Jiro
Technique to synchronize the re-entrant flux reversal of the multiple magnetostrictive Fe77.5Si7.5B15 amorphous wires was developed using a flux keeper of amorphous ribbons contacted to the wire ends. It is comprehended that the characteristics of the re-entrant flux takes place respectively at almost the same time in the three Fe-Si-B amorphous wires with a diameter of 65, 95μm. This phenomenon can be explained by considering the strong magnetic coupling of wires and amorphous ribbon by stray field from the each wire ends. As a result, the magnitude of the induced voltage in the sense coil is increased in proportion to the multiplication of the number of the wires.
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Jensen, K. M.Ø.; Blichfeld, A. B.; Bauers, S. R.; ...
2015-07-05
By means of normal incidence, high flux and high energy x-rays, we have obtained total scattering data for Pair Distribution Function (PDF) analysis from thin films (tf), suitable for local structure analysis. By using amorphous substrates as support for the films, the standard Rapid Acquisition PDF setup can be applied and the scattering signal from the film can be isolated from the total scattering data through subtraction of an independently measured background signal. No angular corrections to the data are needed, as would be the case for grazing incidence measurements. We illustrate the ‘tfPDF’ method through studies of as depositedmore » (i.e. amorphous) and crystalline FeSb 3 films, where the local structure analysis gives insight into the stabilization of the metastable skutterudite FeSb 3 phase. The films were prepared by depositing ultra-thin alternating layers of Fe and Sb, which interdiffuse and after annealing crystallize to form the FeSb 3 structure. The tfPDF data show that the amorphous precursor phase consists of corner-sharing FeSb 6 octahedra with motifs highly resembling the local structure in crystalline FeSb 3. Analysis of the amorphous structure allows predicting whether the final crystalline product will form the FeSb 3 phase with or without excess Sb present. The study thus illustrates how analysis of the local structure in amorphous precursor films can help to understand crystallization processes of metastable phases and opens for a range of new local structure studies of thin films.« less
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Jensen, Kirsten M. Ø.; Blichfeld, Anders B.; Bauers, Sage R.; Wood, Suzannah R.; Dooryhée, Eric; Johnson, David C.; Iversen, Bo B.; Billinge, Simon J. L.
2015-01-01
By means of normal-incidence, high-flux and high-energy X-rays, total scattering data for pair distribution function (PDF) analysis have been obtained from thin films (tf), suitable for local structure analysis. By using amorphous substrates as support for the films, the standard Rapid Acquisition PDF setup can be applied and the scattering signal from the film can be isolated from the total scattering data through subtraction of an independently measured background signal. No angular corrections to the data are needed, as would be the case for grazing incidence measurements. The ‘tfPDF’ method is illustrated through studies of as-deposited (i.e. amorphous) and crystalline FeSb3 films, where the local structure analysis gives insight into the stabilization of the metastable skutterudite FeSb3 phase. The films were prepared by depositing ultra-thin alternating layers of Fe and Sb, which interdiffuse and after annealing crystallize to form the FeSb3 structure. The tfPDF data show that the amorphous precursor phase consists of corner-sharing FeSb6 octahedra with motifs highly resembling the local structure in crystalline FeSb3. Analysis of the amorphous structure allows the prediction of whether the final crystalline product will form the FeSb3 phase with or without excess Sb present. The study thus illustrates how analysis of the local structure in amorphous precursor films can help to understand crystallization processes of metastable phases and opens for a range of new local structure studies of thin films. PMID:26306190
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238U-Series in Fe Oxy/Hydroxides by LA-MC-ICP-MS, New Insights Into Weathering Geochronology
NASA Astrophysics Data System (ADS)
Bernal, J.; McCulloch, M.; Eggins, S.; Grun, R.; Eggleton, R.
2003-12-01
The establishment of a geochronological framework for weathering processes is essential for an understanding of the evolution of the regolith and its dynamics. However, there are few robust answers regarding the absolute age of weathering and its rates. Nowadays, 40Ar/39Ar analysis of Mn-Oxides (cryptomelane) and K-bearing secondary sulphates have provided one of the few generally reliable chronometers (e.g. 1), but is restricted to high-K secondary phases. This work presents a different approach to obtain geochronological information from weathering minerals, namely measurement of 238U-series disequilibria in authigenic Fe oxy/hydroxides. These may be potentially useful recorders of weathering processes as they commonly occur as weathering products and have high affinity towards dissolved uranyl complexes. Furthermore, U-Th fractionation during weathering has been extensively reported [2], effectively resetting the U/230Th geochronometer. LA-MC-ICP-MS facilitates in situ measurement of 238U-series disequilibria in authigenic microcrystalline iron oxy/hydroxides (precipitated between cracks and veins in partially and heavily weathered chlorite-muscovite schist) and pisoliths (ferruginous concretions). Contrary to previous studies [e.g. 3], in situ measurement of 238U-nuclides enables selective analysis or iron oxy/hydroxides phases, minimizes contributions from allogenic phases and, reduces the need of mathematical corrections to obtain the activity ratios for the authigenic phase [4, 5]. The results suggest that supergene iron oxy/hydroxides are good recorders of weathering processes; they precipitate during the early stages of weathering, reflect the U-isotopic composition of the groundwater, appear to act as closed-systems in weathering conservative environments, and behave in a predictable fashion when subjected to intense weathering and leaching conditions. The 230Th-ages of the iron oxy/hydroxides indicate that the timing and intensity of weathering appears to be largely controlled by global climatic changes, suggesting that weathering rates have not been constant during the last 300 ka in Northern Australia. References: 1 P.M. Vasconcelos. Annual Review in Earth and Planetary Sciences 27(1), 183-229, (1999) 2 M. Ivanovich and R.S. Harmon, Uranium-series disequilibrium : applications to earth, marine, and environmental science, xxxiv, 910 pp., Oxford University Press, Oxford, (1992) 3 S.A. Short, R.T. Lowson, J. Ellis and D.M. Price. Geochimica et Cosmochimica Acta 53, 1379-1389, (1989) 4 K.R. Ludwig and D.M. Titterington. Geochimica et Cosmochimica Acta 58(22), 5031-5042, (1994) 5 Luo, S. and T. L. Ku. Geochimica et Cosmochimica Acta 55(2): 555-564. (1991)
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NASA Astrophysics Data System (ADS)
Zhang, Zongyang; Liu, Xiansong; Feng, Shuangjiu; Rehman, Khalid Mehmood Ur
2018-03-01
In this study, the melt spinning method was used to develop Fe80.5Si7.5B6Nb5Cu amorphous ribbons in the first step. Then, the Fe80.5Si7.5B6Nb5Cu amorphous-nanocrystalline core with a compact microstructure was obtained by multiple processes. The main properties of the magnetic powder core, such as micromorphology, thermal behavior, permeability, power loss and quality factor, have been analyzed. The obtained results show that an Fe80.5Si7.5B6Nb5Cu amorphous-nanocrystalline duplex core has high permeability (54.8-57), is relatively stable at different frequencies and magnetic fields, and the maximum power loss is only 313 W/kg; furthermore, it has a good quality factor.
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NASA Astrophysics Data System (ADS)
Henkel, S.; Kasten, S.; Poulton, S.; Hartmann, J.; Staubwasser, M.
2014-12-01
Reactive Fe (oxyhydr)oxides preferentially undergo early diagenetic cycling and may cause a diffusive flux of dissolved Fe2+ from sediments towards the sediment-water interface. The partitioning of Fe in sediments has traditionally been studied by applying sequential extractions based on reductive dissolution of Fe minerals. We complemented the sequential leaching method by Poulton and Canfield [1] in order to be able to gain δ56Fe data for specific Fe fractions, as such data are potentially useful to study Fe cycling in marine environments. The specific mineral fractions are Fe-carbonates, ferrihydrite + lepidocrocite, goethite + hematite, and magnetite. Leaching was performed with acetic acid, hydroxylamine-HCl, Na-dithionite and oxalic acid. The processing of leachates for δ56Fe analysis involved boiling the samples in HCl/HNO3/H2O2, Fe precipitation and anion exchange column chromatography. The new method was applied to short sediment cores from the North Sea and a bay of King George Island (South Shetland Islands, Antarctica). Downcore mineral-specific variations in δ56Fe revealed differing contributions of Fe (oxyhydr)oxides to redox cycling. A slight decrease in easily reducible Fe oxides correlating with a slight increase in δ56Fe for this fraction with depth, which is in line with progessive dissimilatory iron reduction [2,3], is visible in the top 10 cm of the North Sea core, but not in the antarctic sediments. Less reactive (dithionite and oxalate leachable) fractions did not reveal isotopic trends. The acetic acid-soluble fraction displayed pronounced δ56Fe trends at both sites that cannot be explained by acid volatile sulfides that are also extracted by acetic acid [1]. We suggest that low δ56Fe values in this fraction relative to the pool of easily reducible Fe oxides result from adsorbed Fe(II) that was open to isotopic exchange with oxide surfaces, affirming the experimental results of Crosby el al. [2]. Hence, δ56Fe analyses on marine sediments appear to be particularly useful when targeting specific Fe pools, rather than the total highly reactive Fe fraction, since isotopic trends may be masked within the latter pool. [1] Poulton and Canfield (2005), Chemical Geology 214, 209-221. [2] Crosby et al., Geobiology 5 (2007), 169-189. [3] Staubwasser et al., Geology 34 (2006), 629-632.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Thanveer, T.; Thomas, S., E-mail: senoythomas@gmail.com; Ramanujan, R. V.
A study of magnetocaloric effect in amorphous and partially crystallized Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18} alloys is reported. Amorphous Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18}, near its magnetic ordering temperature (600 K) showed a magnetic entropy change ΔS{sub M} of 1.1 J/KgK and a relative cooling power of 36 J/Kg in a field change of 10 kOe. Amorphous samples were partially crystallized by annealing at 700 K at different time intervals. Partially crystallized samples showed two distinct magnetic ordering temperature, one corresponding to the precipitated FeNi nanocrystals and the other one corresponding to the boron rich amorphous matrix. Magnetic ordering temperaturemore » of the residual amorphous matrix got shifted to the lower temperatures on increasing the annealing duration. Partially crystallised samples showed a magnetic entropy change of about 0.27 J/kgK near the magnetic ordering temperature of the amorphous matrix (540 K) in a field change of 10 kOe. The decrease in ΔS{sub M} on partial crystallisation is attributed to the biphasic magnetic nature of the sample.« less
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Solid state amorphization in the Al-Fe binary system during high energy milling
DOE Office of Scientific and Technical Information (OSTI.GOV)
Urban, P., E-mail: purban@us.es; Montes, J. M.; Cintas, J.
2013-12-16
In the present study, mechanical alloying (MA) of Al75Fe25 elemental powders mixture was carried out in argon atmosphere, using a high energy attritor ball mill. The microstructure of the milled products at different stages of milling was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The results showed that the amorphous phase content increased by increasing the milling time, and after 50 hours the amorphization process became complete. Heating the samples resulted in the crystallization of the synthesized amorphous alloys and the appearance of the equilibrium intermetallic compounds Al{sub 5}Fe{submore » 2}.« less
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NASA Astrophysics Data System (ADS)
Jin, Z. Q.; Cui, B. Z.; Liu, J. P.; Ding, Y.; Wang, Z. L.; Thadhani, N. N.
2004-05-01
Pr2Fe14B/α-Fe based nanocomposites have been prepared through crystallization of melt-spun amorphous Pr7Tb1Fe85Nb0.5Zr0.5B6 ribbons by means of ac Joule heating while simultaneously monitoring room-temperature electrical resistance R. The R value shows a strong variation with respect to applied current I, and is closely related to the amorphous-to-nanocrystalline phase transformation. The curve of R versus I allows one to control the crystallization behavior during Joule heating and to identify the heat-treatment conditions for optimum magnetic properties. A coercivity of 550 kA/m and a maximum energy product of 128 kJ/m3 have been obtained upon heating the amorphous ribbons at a current of 2.0 A. These properties are around 30% higher than the values of samples prepared by conventionally (furnace) annealed amorphous ribbons.
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NASA Technical Reports Server (NTRS)
Farrand, W. H.; Harsanyi, Joseph C.
1995-01-01
The success of imaging spectrometry in mineralogic mapping of natural terrains indicates that the technology can also be used to assess the environmental impact of human activities in certain instances. Specifically, this paper describes an investigation into the use of data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) for mapping the spread of, and assessing changes in, the mineralogic character of tailings from a major silver and base metal mining district. The area under investigation is the Coeur d'Alene River Valley in northern Idaho. Mining has been going on in and around the towns of Kellogg and Wallace, Idaho since the 1880's. In the Kellogg-Smelterville Flats area, west of Kellogg, mine tailings were piled alongside the South Fork of the Coeur d'Alene River. Until the construction of tailings ponds in 1968 much of these waste materials were washed directly into the South Fork. The Kellogg-Smelterville area was declared an Environmental Protection Agency (EPA) Superfund site in 1983 and remediation efforts are currently underway. Recent studies have demonstrated that sediments in the Coeur d'Alene River and in the northern part of Lake Coeur d'Alene, into which the river flows, are highly enriched in Ag, Cu, Pb, Zn, Cd, Hg, As, and Sb. These trace metals have become aggregated in iron oxide and oxyhydroxide minerals and/or mineraloids. Reflectance spectra of iron-rich tailing materials are shown. Also shown are spectra of hematite and goethite. The broad bandwidth and long band center (near 1 micron) of the Fe(3+) crystal-field band of the iron-rich sediment samples combined with the lack of features on the Fe(3+) -O(2-) charge transfer absorption edge indicates that the ferric oxide and/or oxyhydroxide in these sediments is poorly crystalline to amorphous in character. Similar features are seen in poorly crystalline basaltic weathering products (e.g., palagonites). The problem of mapping and analyzing the downriver occurrences of iron rich tailings in the Coeur d'Alene (CDA) River Valley using remotely sensed data is complicated by the full vegetation cover present in the area. Because exposures of rock and soil were sparse, the data processing techniques used in this study were sensitive to detecting materials at subpixel scales. The methods used included spectral mixture analysis and a constrained energy minimization technique.
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Aluminium substitution in iron(II-III)-layered double hydroxides: Formation and cationic order
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ruby, Christian; Abdelmoula, Mustapha; Aissa, Rabha
The formation and the modifications of the structural properties of an aluminium-substituted iron(II-III)-layered double hydroxide (LDH) of formula Fe{sub 4}{sup II}Fe{sub (2-6y)}{sup III}Al{sub 6y}{sup III} (OH){sub 12} SO{sub 4}, 8H{sub 2}O are followed by pH titration curves, Moessbauer spectroscopy and high-resolution X-ray powder diffraction using synchrotron radiation. Rietveld refinements allow to build a structural model for hydroxysulphate green rust, GR(SO{sub 4}{sup 2-}), i.e. y=0, in which a bilayer of sulphate anions points to the Fe{sup 3+} species. A cationic order is proposed to occur in both GR(SO{sub 4}{sup 2-}) and aluminium-substituted hydroxysulphate green rust when y<0.08. Variation of the cellmore » parameters and a sharp decrease in average crystal size and anisotropy are detected for an aluminium content as low as y=0.01. The formation of Al-GR(SO{sub 4}{sup 2-}) is preceded by the successive precipitation of Fe{sup III} and Al{sup III} (oxy)hydroxides. Adsorption of more soluble Al{sup III} species onto the initially formed ferric oxyhydroxide may be responsible for this slowdown of crystal growth. Therefore, the insertion of low aluminium amount (y{approx}0.01) could be an interesting way for increasing the surface reactivity of iron(II-III) LDH that maintains constant the quantity of the reactive Fe{sup II} species of the material. - Graphical abstract: (a) Crystallographical structure of sulphated green rust: SO{sub 4}{sup 2-} point to the Fe{sup 3+} cations (red) that form an ordered array with the Fe{sup 2+} cations (green). (b) Width and asymmetry of the synchrotron XRD peaks increase rapidly when some Al{sup 3+} species substitute the Fe{sup 3+} cations; z is molar ratio Al{sup 3+}/Fe{sup 3+}.« less
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Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.
2016-01-01
Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits. PMID:27242685
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Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...
2016-05-10
Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less
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Discrimination among iron sulfide species formed in microbial cultures.
Popa, R; Kinkle, B K
2000-10-01
A quantitative method for the study of iron sulfides precipitated in liquid cultures of bacteria is described. This method can be used to quantify and discriminate among amorphous iron sulfide (FeS(amorph)), iron monosulfide minerals such as mackinawite or greigite (FeS(min)), and iron disulfide minerals such as pyrite or marcasite (FeS(2min)) formed in liquid cultures. Degradation of iron sulfides is performed using a modified Cr(2+) reduction method with reflux distillation. The basic steps of the method are: first, separation of FeS(amorph); second, elimination of interfering species of S such as colloidal sulfur (S(c) degrees ), thiosulphate (S(2)O(3)(2-)) and polysulfides (S(x)(2-)); third, separation of FeS(min); and fourth, separation of FeS(2min). The final product is H(2)S which is determined after trapping. The efficiency of recovery is 96-99% for FeS(amorph), 76-88% for FeS(min), and >97% for FeS(2min). This method has a high reproducibility if the experimental conditions are rigorously applied and only glass conduits are used. A well ventilated fume hood must be used because of the toxicity and volatility of several reagents and products. The advantage relative to previously described methods are better resolution for iron sulfide species and use of the same bottles for both incubation of cultures and acid degradation. The method can also be used for Fe/S stoichiometry with sub-sampling and Fe analysis.
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Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; Knaeble, Alan R.; Marcus, Matthew A.; Lynch, Joshua K.; Toner, Brandy M.
2017-01-01
e of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (lXAS) approach is developed and applied to rotosonic drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s lXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity observed in the distribution of elevated-As wells.
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Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species
NASA Astrophysics Data System (ADS)
Eitel, Eryn M.; Taillefert, Martial
2017-10-01
Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.
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NASA Astrophysics Data System (ADS)
Kalska, B.; Szymański, K.; Dobrzyński, L.; Satuła, D.; Wäppling, R.; Broddefalk, A.; Nordblad, P.
2002-06-01
Properties of amorphous alloy Fe0.66Er0.19B0.15 are reported. A reorientation of the Fe and Er magnetic moments during sample cooling through the compensation point in a large magnetic field is found by means of monochromatic circularly polarised radiation.
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Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena
NASA Astrophysics Data System (ADS)
Zemčík, T.
1994-12-01
Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline “Finemet” alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.
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Kent, D.B.; Davis, J.A.; Anderson, L.C.D.; Rea, B.A.; Coston, J.A.
2002-01-01
Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales. Copyright ?? 2002 Elsevier Science Ltd.
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NASA Astrophysics Data System (ADS)
Yao, Kai; Wu, Xueyan; An, Zhentao
2017-01-01
A flexible shielding fabric with dense uniform coating was prepared after electrical deposition of amorphous Ni-Fe-P and Ni-P alloy on copper-coated polyethylene terephthalate (PET) fabric. The effects of coating composition and the deposition rate were discussed by the current density, temperature and pH value. The morphology, composition, and structure of coating were analyzed by SEM, EDS, and XRD characterizations. The EMI shielding effectiveness and corrosion resistance were also tested. The results fabric possesses dense, smooth, and uniform coating, when the processing conditions are 60°C, pH=1.5, and current density =8.7A/dm2. The coating fabric consists of amorphous Ni-Fe-P alloy with 16.62% P (weight percent), which has excellent of corrosion resistance. By contrast the EMI shielding effectiveness of amorphous Ni-Fe-P was better than amorphous Ni-P. The EMI shielding effectiveness of this coated fabric achieves 69.20dB-80.30dB in a broad frequency range between 300 kHz˜1.5 GHz.
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Determination of local order in the amorphous precursor to Ba-hexaferrite thin-film recording media
NASA Astrophysics Data System (ADS)
Snyder, J. E.; Harris, V. G.; Das, B. N.; Koon, N. C.; Sui, X.; Kryder, M. H.
1996-04-01
Ba-hexaferrite thin films for recording media applications are often fabricated by a two-step process: sputter deposition of an amorphous precursor, followed by annealing to crystallize the BaFe12O19 phase. The magnetic anisotropy of the crystalline films can be either in-plane or perpendicular, depending on the sputtering process used in the first step. However, conventional structural characterization techniques have not been able to distinguish between different as-sputtered films. Using polarization-dependent extended x-ray absorption fine structure (PD-EXAFS), we have observed anisotropic local structure around both Ba and Fe atoms in the amorphous precursor films. Comparison of the results suggests that the amorphous films consist of networks of Fe atoms surrounded by their O nearest neighbors, with Ba atoms fitting into in-between spaces as network modifiers (there might also be some minor Fe network modifying contribution). The local structural anisotropy of the amorphous films appears to determine the orientation of the fast-growing basal plane directions during annealing, and thus the directions of the c axes and the magnetic anisotropy.
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NASA Technical Reports Server (NTRS)
Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.
2017-01-01
Spectroscopic observations of the circumstellar envelopes of evolved O-rich stars indicate the dust is mostly amorphous silicate with olivine-like compositions. Spectral modeling suggests these grains are Fe-rich [Mg/(Mg+Fe) 0.5], but it is not known whether the Fe is distributed within the silicate matrix or exists as metal inclusions. In contrast, the crystalline silicates are inferred to be extremely Mg-rich [Mg/(Mg+Fe) > 0.95]. The mineralogies and chemical compositions of dust in supernova (SN) remnants are not as well constrained, but abundant silicates of olivine-like and enstatite-like compositions have been fit to the infrared emission features. Silicates in the interstellar medium (ISM) are >99% amor-phous and Fe-bearing. The dearth of crystalline silicates in the ISM requires that some amorphization or destruction mechanisms process these grains.
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NASA Astrophysics Data System (ADS)
Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.
2011-11-01
This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.
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NASA Astrophysics Data System (ADS)
Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.
2011-08-01
This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways was evidenced from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions. This shift was promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.
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Timescales of carbon turnover in soils with mixed crystalline mineralogies
NASA Astrophysics Data System (ADS)
Khomo, Lesego; Trumbore, Susan; Bern, Carleton R.; Chadwick, Oliver A.
2017-01-01
Organic matter-mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40-70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9-47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon-mineral interactions.
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Fabrication and Properties of Novel NiWFeB Amorphous Alloys
NASA Astrophysics Data System (ADS)
Zhang, Jiajia; Liu, Wensheng; Ma, Yunzhu; Ye, Xiaoshan; Wu, Yayu
2017-09-01
In this work, we reported the successful synthesis of four quaternary NiWFeB amorphous alloys (Ni53.9W4.3Fe24.2B17.6, Ni49.7W9.7Fe22.3B18.3, Ni46.2W14.1Fe20.8B18.9 and Ni42.2W19.2Fe18.9B19.7 in at.%) via melt spinning method. The synthesized amorphous alloys are characterized by x-ray diffraction, transmission electron microscopy, differential scanning calorimeter, scanning electron microscopy and Vickers indenters. The results showed that the crystallization temperatures T x1 of four amorphous alloys with increased W contents, derived from the exothermic peaks in DSC, were 705, 715, 851, and 965 K, respectively. The Vickers hardness ( H v) of the corresponding four amorphous alloys at room temperature was 8.5, 9.8, 10.3, and 11.4 GPa, respectively. The much finer shear bands in the deformation region underneath the Vickers indenter were observed as the tungsten content increases. All the results showed a tendency that the higher the tungsten content, the greater the thermal stability and hardness. The results indicated the NiWFeB amorphous alloys could be easier fabricated by continuing to increase the tungsten content, and those NiWFeB amorphous alloys would have a promising application in nuclear energies and military defenses.
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Sklute, Elizabeth C; Rogers, A Deanne; Gregerson, Jason C; Jensen, Heidi B; Reeder, Richard J; Dyar, M Darby
2018-03-01
Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multi-component (Fe 2 (SO 4 ) 3 ± Ca, Na, Mg, Fe, Cl, HCO 3 ) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.
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NASA Astrophysics Data System (ADS)
Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby
2018-03-01
Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca-, Na-, Mg- and Fe-chloride brines and multicomponent (Fe2(SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21 °C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe-chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials.
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Mineralogy of Iron Microbial Mats from Loihi Seamount
Toner, Brandy M.; Berquó, Thelma S.; Michel, F. Marc; Sorensen, Jeffry V.; Templeton, Alexis S.; Edwards, Katrina J.
2011-01-01
Extensive mats of Fe oxyhydroxides and associated Fe-oxidizing microbial organisms form in diverse geochemical settings – freshwater seeps to deep-sea vents – where ever opposing Fe(II)-oxygen gradients prevail. The mineralogy, reactivity, and structural transformations of Fe oxyhydroxides precipitated from submarine hydrothermal fluids within microbial mats remains elusive in active and fossil systems. In response, a study of Fe microbial mat formation at the Loihi Seamount was conducted to describe the physical and chemical characteristics of Fe-phases using extended X-ray absorption fine structure spectroscopy, powder X-ray diffraction, synchrotron radiation X-ray total scattering, low-temperature magnetic measurements, and Mössbauer spectroscopy. Particle sizes of 3.5–4.6 nm were estimated from magnetism data, and coherent scattering domain (CSD) sizes as small as 1.6 nm are indicated by pair distribution function (PDF) analysis. Disorder in the nanostructured Fe-bearing phases results in limited intermediate-range structural order: less than that of standard two-line ferrihydrite (Fh), except for the Pohaku site. The short-range ordered natural Fh (FhSRO) phases were stable at 4°C in the presence of oxygen for at least 1 year and during 400°C treatment. The observed stability of the FhSRO is consistent with magnetic observations that point to non-interacting nanoparticles. PDF analyses of total scattering data provide further evidence for FhSRO particles with a poorly ordered silica coating. The presence of coated particles explains the small CSD for the mat minerals, as well as the stability of the minerals over time and against heating. The mineral properties observed here provide a starting point from which progressively older and more extensively altered Fe deposits may be examined, with the ultimate goal of improved interpretation of past biogeochemical conditions and diagenetic processes. PMID:22485113
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NASA Astrophysics Data System (ADS)
Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian
2018-01-01
Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (<60 °C), Fe-rich and H2S-depleted hydrothermal fluids yielded δ56Fe values near +0.1‰, indistinguishable from basalt values. Suspended particles in the vent fluids and FeOx deposits recovered nearby active vents yielded systematically positive δ56Fe values. The enrichment in heavy Fe isotopes between +1.05‰ and +1.43‰ relative to Fe(II) in vent fluids suggest partial oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where they form, and are less sensitive to abiotic versus biotic origins. It follows that FeOx deposits at Loihi Seamount provides important modern analogues for ancient seafloor Fe-rich deposits allowing for testing hypotheses about the biogeochemical cycling of Fe isotopes on early Earth.
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Electron microscopy study of microbial mat in the North Fiji basin hydrothermal vent
NASA Astrophysics Data System (ADS)
Park, H.; Kim, J. W.; Lee, J. W.
2017-12-01
Hydrothermal vent systems consisting of hydrothermal vent, hydrothermal sediment and microbial mat are widely spread around the ocean, particularly spreading axis, continental margin and back-arc basin. Scientists have perceived that the hydrothermal systems, which reflect the primeval earth environment, are one of the best places to reveal the origin of life and extensive biogeochemical process of microbe-mineral interaction. In the present study multiline of analytical methods (X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM)) were utilized to investigate the mineralogy/chemistry of microbe-mineral interaction in hydrothermal microbial mat. Microbial mat samples were recovered by Canadian scientific submersible ROPOS on South Pacific North Fiji basin KIOST hydrothermal vent expedition 1602. XRD analysis showed that red-colored microbial mat contains Fe-oxides and Fe-oxyhydroxides. Various morphologies of minerals in the red-colored microbial mat observed by SEM are mainly showed sheath shaped, resembled with Leptothrix microbial structure, stalks shaped, similar with Marioprofundus microbial structure and globule shaped microbial structures. They are also detected with DNA analysis. The cross sectional observation of microbial structures encrusted with Fe-oxide and Fe-oxyhydroxide at a nano scale by Transmission Electron Microscopy (TEM) and Focused Ion Beam (FIB) technique was developed to verify the structural/biogeochemical properties in the microbe-mineral interaction. Systematic nano-scale measurements on the biomineralization in the microbial mat leads the understandings of biogeochemical environments around the hydrothermal vent.
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Ferromagnetic laser-welded Fe78Si13B9 and Co71.5Fe2.5SigMn2Mo1B14ils amorphous foils
NASA Astrophysics Data System (ADS)
Pawlak, Ryszard
1997-10-01
In the paper the results of attempts at laser welding of amorphous ferromagnetic foils on the iron and cobalt base have been presented. The usefulness of this technology for making small magnetic circuits of metallic glass has been demonstrated. The action of laser radiation leading to rendering the structure amorphous and the infraction of a laser beam with an amorphous material have been discussed. Finally, the results of pulsed welding of a pack of amorphous foils and some properties of the welds formed have been discussed.
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NASA Astrophysics Data System (ADS)
Rodríguez, V. A. Peña; Medina, J. Medina; Marcatoma, J. Quispe; Ayala, Ch. Rojas; Landauro, C. V.; Baggio-Saitovitch, E. M.; Passamani, E. C.
2011-11-01
Nanocrystalline Fe/Zr alloys have been prepared after milling for 9 h the mixture of elemental Fe and Zr powders or the arc-melting produced Fe2Zr alloy by using mechanical alloying and mechanical milling techniques, respectively. X-ray and Mössbauer results of the Fe and Zr powders, mechanically alloyed, suggest that amorphous Fe2Zr phase and \\upalpha-Fe(Zr) nanograins have been produced with relative concentrations of 91% and 9%, respectively. Conversely, the results of the mechanically milled Fe2Zr alloy indicate that nanograins of the Fe2Zr alloy have been formed, surrounded by a magnetic inter-granular phase that are simultaneously dispersed in a paramagnetic amorphous phase.
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NASA Astrophysics Data System (ADS)
Thornton, Steven F.; Tellam, John H.; Lerner, David N.
2000-05-01
The attenuation of inorganic contaminants in acetogenic and methanogenic landfill leachate by calcareous and carbonate-deficient, oxide-rich Triassic sandstone aquifer materials from the English Midlands was examined in laboratory columns. Aqueous equilibrium speciation modelling, simple transport modelling and chemical mass balance approaches are used to evaluate the key processes and aquifer geochemical properties controlling contaminant fate. The results indicate that leachate-rock interactions are dominated by ion-exchange processes, acid-base and redox reactions and sorption/precipitation of metal species. Leachate NH 4 is attenuated by cation exchange with the aquifer sediments; however, NH 4 migration could be described with a simple model using retardation factors. Organic acids in the acetogenic leachate buffered the system pH at low levels during flushing of the calcareous aquifer material. In contrast, equilibrium with Al oxyhydroxide phases initially buffered pH (˜4.5) during flushing of the carbonate-deficient sandstone with methanogenic leachate. This led to the mobilisation of sorbed and oxide-bound heavy metals from the aquifer sediment which migrated as a concentrated pulse at the leachate front. Abiotic reductive dissolution of Mn oxyhydroxides on each aquifer material by leachate Fe 2+ maintains high concentrations of dissolved Mn and buffers the leachate inorganic redox system. This feature is analogous to the Mn-reducing zones found in leachate plumes and in the experiments provides a sink for the leachate Fe load and other heavy metals. The availability of reactive solid phase Mn oxyhydroxides limits the duration of redox buffering and Fe attenuation by these aquifer sediments. Aquifer pH and redox buffering capacity exert a fundamental influence on leachate inorganic contaminant fate in these systems. The implications for the assessment of aquifer vulnerability at landfills are discussed and simple measurements of aquifer properties which may improve the prediction of contaminant attenuation are outlined.
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NASA Astrophysics Data System (ADS)
Hein, James R.; Koski, Randolph A.
1987-08-01
Numerous manganese deposits in the Franciscan Complex, California, occur as conformable lenses within bedded radiolarian chert-argillite sequences that are, in turn, intercalated within thicker sections of sandstone and shale. The field relations, composition, and petro-graphic and isotopic characteristics indicate that the manganese was concentrated by diagenetic reconstitution of siliceous and hemipelagic sediment during burial. The ore lenses are Mn-rich and Fe-poor assemblages consisting largely of rhodochrosite, manganese silicates, opal-CT (disordered cristobalite-tridymite), and quartz. Highly negative δ13C values for the carbonate carbon in rhodochrosite indicate that CO2 likely originated from oxidation of methane; less negative values result from mixing of methanogenic carbon and CO2 derived from bacterial degradation of organic matter. The δ18O values for the carbonate of rhodochrosite indicate temperatures of formation between 12 and 100 °C. The oxidation of methane prior to carbonate precipitation may have used the minor (0.4% 0.5%) Mn and Fe oxyhydroxides and oxides deposited with the sediment. The mobilization of manganese from biogenic and terrigenous sources in the sediment column into discrete horizons and the fractioriation of manganese from iron reflect the presence of oxidation-reduction boundaries and gradients in the sediment column. Fluids derived from compaction and silica-dehydration reactions in the transformation of opal-A (X-ray amorphous biogenic silica) to quartz were involved in transportation of principal components. Sedimentary and geochemical attributes suggest that the deposits formed in a deep-water environment in a zone of oceanic upwelling near a continental margin.
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Chan, Marjorie A.; McPherson, Brian J.
2014-01-01
Abstract Iron (oxyhydr)oxide microbial mats in modern to ∼100 ka tufa terraces are present in a cold spring system along Ten Mile Graben, southeastern Utah, USA. Mats exhibit morphological, chemical, and textural biosignatures and show diagenetic changes that occur over millennial scales. The Jurassic Brushy Basin Member of the Morrison Formation in the Four Corners region of the USA also exhibits comparable microbial fossils and iron (oxyhydr)oxide biosignatures in the lacustrine unit. Both the modern spring system and Brushy Basin Member represent alkaline, saline, groundwater-fed systems and preserve diatoms and other similar algal forms with cellular elaboration. Two distinct suites of elements (1. C, Fe, As and 2. C, S, Se, P) are associated with microbial fossils in modern and ancient iron (oxyhydr)oxides and may be potential markers for biosignatures. The presence of ferrihydrite in ∼100 ka fossil microbial mats and Jurassic rocks suggests that this thermodynamically unstable mineral may also be a potential biomarker. One of the most extensive sedimentary records on Mars is exposed in Gale Crater and consists of non-acidic clays and sulfates possibly of lacustrine origin. These terrestrial iron (oxyhydr)oxide examples are a valuable analogue because of similar iron- and clay-rich host rock compositions and will help (1) understand diagenetic processes in a non-acidic, saline lacustrine environment such as the sedimentary rocks in Gale Crater, (2) document specific biomediated textures, (3) demonstrate how biomediated textures might persist or respond to diagenesis over time, and (4) provide a ground truth library of textures to explore and compare in extraterrestrial iron (oxyhydr)oxides, where future explorations hope to detect past evidence of life. Key Words: Biogeochemistry—Mars—Biosignatures—Diagenesis—Iron oxides. Astrobiology 14, 1–14. PMID:24380534
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Novel Pelagic Iron-Oxidizing Zetaproteobacteria from the Chesapeake Bay Oxic-Anoxic Transition Zone.
Chiu, Beverly K; Kato, Shingo; McAllister, Sean M; Field, Erin K; Chan, Clara S
2017-01-01
Chemolithotrophic iron-oxidizing bacteria (FeOB) could theoretically inhabit any environment where Fe(II) and O 2 (or nitrate) coexist. Until recently, marine Fe-oxidizing Zetaproteobacteria had primarily been observed in benthic and subsurface settings, but not redox-stratified water columns. This may be due to the challenges that a pelagic lifestyle would pose for Zetaproteobacteria, given low Fe(II) concentrations in modern marine waters and the possibility that Fe oxyhydroxide biominerals could cause cells to sink. However, we recently cultivated Zetaproteobacteria from the Chesapeake Bay oxic-anoxic transition zone, suggesting that they can survive and contribute to biogeochemical cycling in a stratified estuary. Here we describe the isolation, characterization, and genomes of two new species, Mariprofundus aestuarium CP-5 and Mariprofundus ferrinatatus CP-8, which are the first Zetaproteobacteria isolates from a pelagic environment. We looked for adaptations enabling strains CP-5 and CP-8 to overcome the challenges of living in a low Fe redoxcline with frequent O 2 fluctuations due to tidal mixing. We found that the CP strains produce distinctive dreadlock-like Fe oxyhydroxide structures that are easily shed, which would help cells maintain suspension in the water column. These oxides are by-products of Fe(II) oxidation, likely catalyzed by the putative Fe(II) oxidase encoded by the cyc2 gene, present in both CP-5 and CP-8 genomes; the consistent presence of cyc2 in all microaerophilic FeOB and other FeOB genomes supports its putative role in Fe(II) oxidation. The CP strains also have two gene clusters associated with biofilm formation (Wsp system and the Widespread Colonization Island) that are absent or rare in other Zetaproteobacteria. We propose that biofilm formation enables the CP strains to attach to FeS particles and form flocs, an advantageous strategy for scavenging Fe(II) and developing low [O 2 ] microenvironments within more oxygenated waters. However, the CP strains appear to be adapted to somewhat higher concentrations of O 2 , as indicated by the presence of genes encoding aa 3 -type cytochrome c oxidases, but not the cbb 3 -type found in all other Zetaproteobacteria isolate genomes. Overall, our results reveal adaptations for life in a physically dynamic, low Fe(II) water column, suggesting that niche-specific strategies can enable Zetaproteobacteria to live in any environment with Fe(II).
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Novel Pelagic Iron-Oxidizing Zetaproteobacteria from the Chesapeake Bay Oxic–Anoxic Transition Zone
Chiu, Beverly K.; Kato, Shingo; McAllister, Sean M.; Field, Erin K.; Chan, Clara S.
2017-01-01
Chemolithotrophic iron-oxidizing bacteria (FeOB) could theoretically inhabit any environment where Fe(II) and O2 (or nitrate) coexist. Until recently, marine Fe-oxidizing Zetaproteobacteria had primarily been observed in benthic and subsurface settings, but not redox-stratified water columns. This may be due to the challenges that a pelagic lifestyle would pose for Zetaproteobacteria, given low Fe(II) concentrations in modern marine waters and the possibility that Fe oxyhydroxide biominerals could cause cells to sink. However, we recently cultivated Zetaproteobacteria from the Chesapeake Bay oxic–anoxic transition zone, suggesting that they can survive and contribute to biogeochemical cycling in a stratified estuary. Here we describe the isolation, characterization, and genomes of two new species, Mariprofundus aestuarium CP-5 and Mariprofundus ferrinatatus CP-8, which are the first Zetaproteobacteria isolates from a pelagic environment. We looked for adaptations enabling strains CP-5 and CP-8 to overcome the challenges of living in a low Fe redoxcline with frequent O2 fluctuations due to tidal mixing. We found that the CP strains produce distinctive dreadlock-like Fe oxyhydroxide structures that are easily shed, which would help cells maintain suspension in the water column. These oxides are by-products of Fe(II) oxidation, likely catalyzed by the putative Fe(II) oxidase encoded by the cyc2 gene, present in both CP-5 and CP-8 genomes; the consistent presence of cyc2 in all microaerophilic FeOB and other FeOB genomes supports its putative role in Fe(II) oxidation. The CP strains also have two gene clusters associated with biofilm formation (Wsp system and the Widespread Colonization Island) that are absent or rare in other Zetaproteobacteria. We propose that biofilm formation enables the CP strains to attach to FeS particles and form flocs, an advantageous strategy for scavenging Fe(II) and developing low [O2] microenvironments within more oxygenated waters. However, the CP strains appear to be adapted to somewhat higher concentrations of O2, as indicated by the presence of genes encoding aa3-type cytochrome c oxidases, but not the cbb3-type found in all other Zetaproteobacteria isolate genomes. Overall, our results reveal adaptations for life in a physically dynamic, low Fe(II) water column, suggesting that niche-specific strategies can enable Zetaproteobacteria to live in any environment with Fe(II). PMID:28769885
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Nuclear Waste Package Mockups: A Study of In-situ Redox State
NASA Astrophysics Data System (ADS)
Helean, K.; Anderson, B.; Brady, P. V.
2006-05-01
The Yucca Mountain Repository (YMR), located in southern Nevada, is to be the first facility in the U.S. for the permanent disposal of high-level radioactive waste and spent nuclear fuels. Total system performance assessment(TSPA) has indicated that among the major radionuclides contributing to dose are Np, Tc, and I. These three radionuclides are mobile in most geochemical settings, and therefore sequestering them within the repository horizon is a priority for the Yucca Mountain Project (YMP). Corroding steel may offset radionuclide transport processes within the proposed waste packages at YMR by retaining radionuclides, creating locally reducing conditions, and reducing porosity. Ferrous iron has been shown to reduce UO22+ to UO2s, and some ferrous iron-bearing ion-exchange materials have been shown to adsorb radionuclides and heavy metals. Locally reducing conditions may lead to the reduction and subsequent immobilization of problematic dissolved species such as TcO4-, NpO2+, and UO22+ and can also inhibit corrosion of spent nuclear fuel. Water occluded during corrosion produces bulky corrosion products, and consequently less porosity is available for water and radionuclide transport. The focus of this study is on the nature of Yucca Mountain waste package corrosion products and their effects on local redox conditions, radionuclide transport, and porosity. In order to measure in-situ redox, six small-scale (1:40) waste package mockups were constructed using A516 and 316 stainless steel, the same materials as the proposed Yucca Mountain waste packages. The mockups are periodically injected with a simulated groundwater and the accumulated effluent and corrosion products are evaluated for their Fe(II)/Fe(III) content and mineralogy. Oxygen fugacities are then calculated and, thus, in-situ redox conditions are determined. Early results indicate that corrosion products are largely amorphous Fe-oxyhydroxides, goethite and magnetite. That information together with the measured Fe(II)/Fe(III) ratios in the mockup effluent constrain the oxygen fugacity to approximately 10-38 atm, many orders of magnitude below ambient. These results and their impact on radionuclide migration from YMR will be discussed.
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NASA Astrophysics Data System (ADS)
Leybourne, Matthew I.; Johannesson, Karen H.
2008-12-01
We have collected ˜500 stream waters and associated bed-load sediments over an ˜400 km 2 region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into "dissolved" (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm] NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce ∗] NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu ∗] NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm] NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb] NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce ∗] NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu ∗] NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm] NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb] NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced. The partial extraction recovered, on average ˜20% of the Fe in the total sediment, ˜80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO 2/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.
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NASA Technical Reports Server (NTRS)
Achilles, C. N.; Downs, R. T.; Rampe, E. B.; Morris, R. V.; Bristow, T. F.; Ming, D. W.; Blake, D. F.; Vaniman, D. T.; Morrison, S. M.; Sutter, B.;
2017-01-01
The Mars Science Laboratory rover, Curiosity, is exploring the lowermost formation of Gale crater's central mound. Within this formation, three samples named Marimba, Quela, and Sebina have been analyzed by the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS) to determine mineralogy and bulk elemental chemistry, respectively. Marimba and Quela were also analyzed by the SAM (Sample Analysis at Mars) instrument to characterize the type and abundance of volatile phases detected in evolved gas analyses (EGA). CheMin data show similar proportions of plagioclase, hematite, and Ca-sulfates along with a mixture of di- and trioctahedral smectites at abundances of approximately 28, approximately 16, and approximately 18 wt% for Marimba, Quela, and Sebina. Approximately 50 wt% of each mudstone is comprised of X-ray amorphous and trace crystalline phases present below the CheMin detection limit (approximately 1 wt%). APXS measurements reveal a distinct bulk elemental chemistry that cannot be attributed to the clay mineral variation alone indicating a variable amorphous phase assemblage exists among the three mudstones. To explore the amorphous component, the calculated amorphous composition and SAM EGA results are used to identify amorphous phases unique to each mudstone. For example, the amorphous fraction of Marimba has twice the FeO wt% compared to Quela and Sebina yet, SAM EGA data show no evidence for Fe-sulfates. These data imply that Fe must reside in alternate Fe-bearing amorphous phases (e.g., nanophase iron oxides, ferrihydrite, etc.). Constraining the composition, abundances, and proposed identity of the amorphous fraction provides an opportunity to speculate on the past physical, chemical, and/or diagenetic processes which produced such phases in addition to sediment sources, lake chemistry, and the broader geologic history of Gale crater.
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NASA Astrophysics Data System (ADS)
Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan
2018-02-01
The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.
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NASA Astrophysics Data System (ADS)
Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III
2006-11-01
The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.
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Synthesis of FeCoB amorphous nanoparticles and application in ferrofluids
NASA Astrophysics Data System (ADS)
Zhao, Shuchun; Bian, Xiufang; Yang, Chuncheng; Yu, Mengchun; Wang, Tianqi
2018-03-01
Magnetic FeCoB amorphous nanoparticles were successfully synthesized by borohydride reduction in water/n-hexane (W/He) microemulsions. The as-prepared FeCoB alloys are amorphous and spherical nanoparticles with an average particle size about 10.7 nm, compared to FeCoB alloys with an average particle size about 304.2 nm which were synthesized by a conventional aqua-solution method. Furthermore, three kinds of FeCoB ferrofluids (FFs) were prepared by dispersing FeCoB particles into W/He microemulsion, water and silicone oil respectively. Results show that the W/He-based FeCoB FFs are superparamagnetic with saturation magnetization (Ms) reaching to 12.4 emu/g. Besides, compared to water-based and silicone oil-based FFs, W/He-based FeCoB FFs exhibit high stability, with magnetic weights decreasing slightly even under the magnetic field intensity of H = 210 mT. In the W/He-based FeCoB FFs, interfacial tensions of water phase and oil phase are supposed to prevent the agglomeration and sedimentation of FeCoB nanoparticles dispersed in different water droplets of the microemulsion, compared to the current stabilizing method of directly modifying the surface of particles.
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Amorphous surface layers in Ti-implanted Fe
DOE Office of Scientific and Technical Information (OSTI.GOV)
Knapp, J.A.; Follstaedt, D.M.; Picraux, S.T.
1979-01-01
Implanting Ti into high-purity Fe results in an amorphous surface layer which is composed of not only Fe and Ti, but also C. Implantations were carried out at room temperature over the energy range 90 to 190 keV and fluence range 1 to 2 x 10/sup 16/ at/cm/sup 2/. The Ti-implanted Fe system has been characterized using transmission electron microscopy (TEM), ion backscattering and channeling analysis, and (d,p) nuclear reaction analysis. The amorphous layer was observed to form at the surface and grow inward with increasing Ti fluence. For an implant of 1 x 10/sup 17/ Ti/cm/sup 2/ at 180more » keV the layer thickness was 150 A, while the measured range of the implanted Ti was approx. 550 A. This difference is due to the incorporation of C into the amorphous alloy by C being deposited on the surface during implantation and subsequently diffusing into the solid. Our results indicate that C is an essential constituent of the amorphous phase for Ti concentrations less than or equal to 10 at. %. For the 1 x 10/sup 17/ Ti/cm/sup 2/ implant, the concentration of C in the amorphous phase was approx. 25 at. %, while that of Ti was only approx. 3 at. %. A higher fluence implant of 2 x 10/sup 17/ Ti/cm/sup 2/ produced an amorphous layer with a lower C concentration of approx. 10 at. % and a Ti concentration of approx. 20 at. %.« less
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Préat, Alain R; de Jong, Jeroen T M; Mamet, Bernard L; Mattielli, Nadine
2008-08-01
The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.
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Exchange bias and bistable magneto-resistance states in amorphous TbFeCo thin films
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Xiaopu, E-mail: xl6ba@virginia.edu; Ma, Chung T.; Poon, S. Joseph, E-mail: sjp9x@virginia.edu
2016-01-04
Amorphous TbFeCo thin films sputter deposited at room temperature on thermally oxidized Si substrate are found to exhibit strong perpendicular magnetic anisotropy. Atom probe tomography, scanning transmission electron microscopy, and energy dispersive X-ray spectroscopy mapping have revealed two nanoscale amorphous phases with different Tb atomic percentages distributed within the amorphous film. Exchange bias accompanied by bistable magneto-resistance states has been uncovered near room temperature by magnetization and magneto-transport measurements. The exchange anisotropy originates from the exchange interaction between the ferrimagnetic and ferromagnetic components corresponding to the two amorphous phases. This study provides a platform for exchange bias and magneto-resistance switchingmore » using single-layer amorphous ferrimagnetic thin films that require no epitaxial growth.« less
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Channel scaling and field-effect mobility extraction in amorphous InZnO thin film transistors
NASA Astrophysics Data System (ADS)
Lee, Sunghwan; Song, Yang; Park, Hongsik; Zaslavsky, A.; Paine, D. C.
2017-09-01
Amorphous oxide semiconductors (AOSs) based on indium oxides are of great interest for next generation ultra-high definition displays that require much smaller pixel driving elements. We describe the scaling behavior in amorphous InZnO thin film transistors (TFTs) with a significant decrease in the extracted field-effect mobility μFE with channel length L (from 39.3 to 9.9 cm2/V·s as L is reduced from 50 to 5 μm). Transmission line model measurements reveal that channel scaling leads to a significant μFE underestimation due to contact resistance (RC) at the metallization/channel interface. Therefore, we suggest a method of extracting correct μFE when the TFT performance is significantly affected by RC. The corrected μFE values are higher (45.4 cm2/V·s) and nearly independent of L. The results show the critical effect of contact resistance on μFE measurements and suggest strategies to determine accurate μFE when a TFT channel is scaled.
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Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong
Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less
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Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces
Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong; ...
2017-09-26
Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less
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Atomic mixing induced by swift heavy ion irradiation of Fe/Zr multilayers
NASA Astrophysics Data System (ADS)
Jaouen, C.; Michel, A.; Pacaud, J.; Dufour, C.; Bauer, Ph.; Gervais, B.
1999-01-01
The mechanism of ion induced mixing and phase change was studied for Fe/Zr multilayers, and specifically for the case of swift heavy ions giving rise to a very large electronic excitation of the target. The multilayers had a modulation of 7.6 nm and an overall composition Fe 69Zr 31. The Zr layers were amorphous whereas the Fe ones were crystalline (bcc) with a very strong (1 1 0) texture in the growth direction. The phase transformation and the composition changes were analysed using the structural and magnetic properties of the Fe component by means of a detailed analysis of the X-ray diffraction profiles and with the aid of backscattering Mössbauer spectroscopy. A complete mixing was observed at a fluence of 10 13 U/cm 2. Both phenomena, the dose dependence of the ion beam mixed amorphous non-magnetic phase and the quantitative evolution of the crystalline iron layer thickness, suggest that mixing occurs in a two-stage process. At an initial stage, an anisotropic diffusion of iron atoms in the amorphous zirconium layers takes place along the interface, while subsequent ion bombardment leads to a generalised transformation through the whole of the Fe layer. Finally, the implications of these observations are discussed in comparison to the plastic deformation phenomena reported for amorphous alloys.
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Dickmann, Robin S; Strasburg, Gale M; Romsos, Dale R; Wilson, Lori A; Lai, Grace H; Huang, Hsimin
2016-03-01
Ferric orthophosphate (FePO₄) has had limited use as an iron fortificant in ready-to-eat (RTE) cereal because of its variable bioavailability, the mechanism of which is poorly understood. Even though FePO₄ has desirable sensory properties as compared to other affordable iron fortificants, few published studies have well-characterized its physicochemical properties. Semi-crystalline materials such as FePO₄ have varying degrees of molecular disorder, referred to as amorphous content, which is hypothesized to be an important factor in bioavailability. The objective of this study was to systematically measure the physicochemical factors of particle size, surface area, amorphous content, and solubility underlying the variation in FePO₄ bioavailability. Five commercial FePO₄ sources and ferrous sulfate were added to individual batches of RTE cereal. The relative bioavailability value (RBV) of each iron source, determined using the AOAC Rat Hemoglobin Repletion Bioassay, ranged from 51% to 99% (p < 0.05), which is higher than typically reported. Solubility in dilute HCl accurately predicted RBV (R² = 0.93, p = 0.008). Amorphous content measured by Dynamic Vapor Sorption ranged from 1.7% to 23.8% and was a better determinant of solubility (R² = 0.91; p = 0.0002) than surface area (R² = 0.83; p = 0.002) and median particle size (R² = 0.59; p = 0.12). The results indicate that while solubility of FePO₄ is highly predictive of RBV, solubility, in turn, is strongly linked to amorphous content and surface area. This information may prove useful for the production of FePO₄ with the desired RBV.
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Dickmann, Robin S.; Strasburg, Gale M.; Romsos, Dale R.; Wilson, Lori A.; Lai, Grace H.; Huang, Hsimin
2016-01-01
Ferric orthophosphate (FePO4) has had limited use as an iron fortificant in ready-to-eat (RTE) cereal because of its variable bioavailability, the mechanism of which is poorly understood. Even though FePO4 has desirable sensory properties as compared to other affordable iron fortificants, few published studies have well-characterized its physicochemical properties. Semi-crystalline materials such as FePO4 have varying degrees of molecular disorder, referred to as amorphous content, which is hypothesized to be an important factor in bioavailability. The objective of this study was to systematically measure the physicochemical factors of particle size, surface area, amorphous content, and solubility underlying the variation in FePO4 bioavailability. Five commercial FePO4 sources and ferrous sulfate were added to individual batches of RTE cereal. The relative bioavailability value (RBV) of each iron source, determined using the AOAC Rat Hemoglobin Repletion Bioassay, ranged from 51% to 99% (p < 0.05), which is higher than typically reported. Solubility in dilute HCl accurately predicted RBV (R2 = 0.93, p = 0.008). Amorphous content measured by Dynamic Vapor Sorption ranged from 1.7% to 23.8% and was a better determinant of solubility (R2 = 0.91; p = 0.0002) than surface area (R2 = 0.83; p = 0.002) and median particle size (R2 = 0.59; p = 0.12). The results indicate that while solubility of FePO4 is highly predictive of RBV, solubility, in turn, is strongly linked to amorphous content and surface area. This information may prove useful for the production of FePO4 with the desired RBV. PMID:26938556
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Fractionation of Fe isotopes by soil microbes and organic acids
Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.
2001-01-01
Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.
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Trace metal concentrations in tropical mangrove sediments, NE Brazil.
Miola, Brígida; Morais, Jáder Onofre de; Pinheiro, Lidriana de Souza
2016-01-15
Sediment cores were taken from the mangroves of the Coreaú River estuary off the northeast coast of Brazil. They were analyzed for grain size, CaCO3, organic matter, and trace metal (Cd, Pb, Zn, Cu, Al, and Fe) contents. Mud texture was the predominant texture. Levels of trace metals in surface sediments indicated strong influence of anthropogenic processes, and diagenetic processes controlled the trace metal enrichment of core sediments of this estuary. The positive relationships between trace metals and Al and Fe indicate that Cu, Zn, Pb, and Cd concentrations are associated mainly with Al and Fe oxy-hydroxides and have natural sources. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation
Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.
2006-01-01
Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record. ?? 2005 Elsevier Inc. All rights reserved.
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Timescales of carbon turnover in soils with mixed crystalline mineralogies
Khomo, Lesego; Trumbore, Susan E.; Bern, Carleton R.; Chadwick, Oliver A.
2017-01-01
Organic matter–mineral associations stabilize much of the carbon (C) stored globally in soils. Metastable short-range-order (SRO) minerals such as allophane and ferrihydrite provide one mechanism for long-term stabilization of organic matter in young soil. However, in soils with few SRO minerals and a predominance of crystalline aluminosilicate or Fe (and Al) oxyhydroxide, C turnover should be governed by chemisorption with those minerals. Here, we correlate mineral composition from soils containing small amounts of SRO minerals with mean turnover time (TT) of C estimated from radiocarbon (14C) in bulk soil, free light fraction and mineral-associated organic matter. We varied the mineral amount and composition by sampling ancient soils formed on different lithologies in arid to subhumid climates in Kruger National Park (KNP), South Africa. Mineral contents in bulk soils were assessed using chemical extractions to quantify Fe oxyhydroxides and SRO minerals. Because of our interest in the role of silicate clay mineralogy, particularly smectite (2 : 1) and kaolinite (1 : 1), we separately quantified the mineralogy of the clay-sized fraction using X-ray diffraction (XRD) and measured 14C on the same fraction. Density separation demonstrated that mineral associated C accounted for 40–70 % of bulk soil organic C in A and B1 horizons for granite, nephelinite and arid-zone gabbro soils, and > 80 % in other soils. Organic matter strongly associated with the isolated clay-sized fraction represented only 9–47 % of the bulk soil C. The mean TT of C strongly associated with the clay-sized fraction increased with the amount of smectite (2 : 1 clays); in samples with > 40 % smectite it averaged 1020 ± 460 years. The C not strongly associated with clay-sized minerals, including a combination of low-density C, the C associated with minerals of sizes between 2 µm and 2 cm (including Fe oxyhydroxides as coatings), and C removed from clay-sized material by 2 % hydrogen peroxide had TTs averaging 190 ± 190 years in surface horizons. Summed over the bulk soil profile, we found that smectite content correlated with the mean TT of bulk soil C across varied lithologies. The SRO mineral content in KNP soils was generally very low, except for the soils developed on gabbros under more humid climate that also had very high Fe and C contents with a surprisingly short, mean C TTs. In younger landscapes, SRO minerals are metastable and sequester C for long timescales. We hypothesize that in the KNP, SRO minerals represent a transient stage of mineral evolution and therefore lock up C for a shorter time. Overall, we found crystalline Fe-oxyhydroxides (determined as the difference between Fe in dithionate citrate and oxalate extractions) to be the strongest predictor for soil C content, while the mean TT of soil C was best predicted from the amount of smectite, which was also related to more easily measured bulk properties such as cation exchange capacity or pH. Combined with previous research on C turnover times in 2 : 1 vs. 1 : 1 clays, our results hold promise for predicting C inventory and persistence based on intrinsic timescales of specific carbon–mineral interactions.
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NASA Astrophysics Data System (ADS)
Weiss, J. V.; Megonigal, J. P.; Emerson, D.
2002-05-01
We have found that the Fe-oxide deposits (Fe-plaque) on wetland plant roots contain abundant microbes including Fe(II)-oxidizing bacteria (FeOB) (Appl. Environ. Microbiol. 1999, 65:2758-2761). In the current study, we investigated the potential for root Fe-plaque to serve as a substrate for Fe(III)-reducing bacteria (FeRB) and compared rates of Fe reduction between plaque and bulk soil. In a study at six wetland habitats located in the Mid-Atlantic region, abundances of FeRB in the rhizosphere of Typha spp. and the bulk soil were enumerated using the most probable number technique. In the rhizosphere, FeRB accounted for an average of 12% of the total cell number while in the soil they accounted for <1% of the total bacteria. We subsequently performed a sequential chemical extraction on both roots and soil to determine if FeRB abundances were driven by differences in the reducibility of Fe(III) in each environment. The roots contained a significantly higher percentage of amorphous Fe (77.4%; p<0.05 n=5 wetlands) than the bulk soil (33.8%); conversely, the soil also had significantly higher amounts of crystalline Fe (41.1%, p<0.05, n=5 wetlands) than the roots (8.1%). A significant correlation was observed between the percentage of amorphous Fe and the percentage of FeRB (r2=0.583; p<0.05). Since amorphous Fe is more readily reduced by microbes than crystalline Fe, these results suggested that the roots provide a good substrate for iron-reducing bacteria. To determine how differences in reducible Fe(III) might limit Fe reduction potential, we performed 12-day anaerobic incubations of roots and soil with Geobacter metallireducans, a common FeRB isolated from aquatic environments. Although Fe(III) reduction rates peaked at between 48 and 72 hours in both the roots and soils, the total amount of Fe(II) production in the root samples was significantly higher than that in the soil samples (350 μ moles g dry weight-1 vs. 153 μ moles g dry weight-1; p<0.05). All of these findings, including higher percentages of FeRB and amorphous Fe in the rhizosphere than in the bulk soil, support the hypothesis that the wetland plant rhizosphere is an active zone of Fe(III) reduction.
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Aqueous formation and manipulation of the iron-oxo Keggin ion
NASA Astrophysics Data System (ADS)
Sadeghi, Omid; Zakharov, Lev N.; Nyman, May
2015-03-01
There is emerging evidence that growth of synthetic and natural phases occurs by the aggregation of prenucleation clusters, rather than classical atom-by-atom growth. Ferrihydrite, an iron oxyhydroxide mineral, is the common form of Fe3+ in soils and is also in the ferritin protein. We isolated a 10 angstrom discrete iron-oxo cluster (known as the Keggin ion, Fe13) that has the same structural features as ferrihydrite. The stabilization and manipulation of this highly reactive polyanion in water is controlled exclusively by its counterions. Upon dissolution of Fe13 in water with precipitation of its protecting Bi3+-counterions, it rapidly aggregates to ~22 angstrom spherical ferrihydrite nanoparticles. Fe13 may therefore also be a prenucleation cluster for ferrihydrite formation in natural systems, including by microbial and cellular processes.
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Shock wave induced phase transition in α -FePO 4
NASA Astrophysics Data System (ADS)
Joshi, K. D.; Suresh, N.; Jyoti, G.; Kulshreshtha, S. K.; Gupta, S. C.; Sikka, S. K.
Shock wave induced response of the berlinite form of FePO 4 has been investigated up to 8.5 GPa. The X-ray diffraction measurements on the shock recovered samples reveal transition to the mixture of an amorphous phase and an orthorhombic phase around 5 GPa. The proportion of the amorphous material in the recovered sample is found to decrease at higher pressure. The results are interpreted in terms of a three-level free energy diagram for the crystal to amorphous transitions.
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Sm5(Fe,Ti)17 melt-spun ribbons with high coercivity
NASA Astrophysics Data System (ADS)
Saito, Tetsuji; Horita, Toru
2018-05-01
It has previously been reported that annealing of amorphous Sm5Fe17 melt-spun ribbon resulted in the formation of the Sm5Fe17 phase and the resultant Sm5Fe17 melt-spun ribbon exhibited a high coercivity. However, the annealing condition of the amorphous Sm5Fe17 melt-spun ribbon was somewhat critical and it was not easy to obtain Sm5Fe17 grains with high coercivity. In the present study, it was found that the small substitution of Ti for Fe in the Sm5Fe17 melt-spun ribbon stabilized the Sm5Fe17 phase. Annealed Sm5Fe16.7Ti0.3 melt-spun ribbon consisted of small and homogeneous Sm5(Fe,Ti)17 grains and exhibited a higher coercivity than the annealed Sm5Fe17 melt-spun ribbon.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Cances, Benjamin; Benedetti, Marc; Farges, Francois
2007-02-02
Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands atmore » pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Cances, Benjamin; /Marne La Vallee U.; Benedetti, Marc
2006-12-13
Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OHmore » ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less
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High temperature coercive field behavior of Fe-Zr powder
NASA Astrophysics Data System (ADS)
Mishra, Debabrata; Perumal, A.; Srinivasan, A.
2009-04-01
We report the investigation of high temperature coercive field behavior of Fe80Zr20 nanocrystalline alloy powder having two-phase microstructure prepared by mechanical alloying process. Thermomagnetization measurement shows the presence of two different magnetic phase transitions corresponding to the amorphous matrix and nonequilibrium Fe(Zr) solid solution. Temperature dependent coercivity exhibits a sharp increase in its value close to the Curie temperature of the amorphous matrix. This feature is attributed to the loss of intergranular ferromagnetic exchange coupling between the nanocrystallites due to the paramagnetic nature of the amorphous matrix. The temperature dependent coercive field behavior is ascribed to the variations in both the effective anisotropy and the exchange stiffness constant with temperature.
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NASA Astrophysics Data System (ADS)
Poulton, Simon W.; Canfield, Donald E.
2006-12-01
We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ˜19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ˜12 m. Molar P/Fe ratios are then relatively constant to a depth of ˜35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.
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Microstructure, soft magnetic properties and applications of amorphous Fe-Co-Si-B-Mo-P alloy
NASA Astrophysics Data System (ADS)
Hasiak, Mariusz; Miglierini, Marcel; Łukiewski, Mirosław; Łaszcz, Amadeusz; Bujdoš, Marek
2018-05-01
DC thermomagnetic properties of Fe51Co12Si16B8Mo5P8 amorphous alloy in the as-quenched and after annealing below crystallization temperature are investigated. They are related to deviations in the microstructure as revealed by Mössbauer spectrometry. Study of AC magnetic properties, i.e. hysteresis loops, relative permeability and core losses versus maximum induction was aimed at obtaining optimal initial parameters for simulation process of a resonant transformer for a rail power supply converter. The results obtained from numerical analyses including core losses, winding losses, core mass, and dimensions were compared with the same parameters calculated for Fe-Si alloy and ferrite. Moreover, Steinmetz coefficients were also calculated for the as-quenched Fe51Co12Si16B8Mo5P8 amorphous alloy.
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Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.
Dold, Bernhard; Blowes, David W; Dickhout, Ralph; Spangenberg, Jorge E; Pfeifer, Hans-Rudolf
2005-04-15
The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies.
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NASA Astrophysics Data System (ADS)
Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.
2001-07-01
Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.
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NASA Astrophysics Data System (ADS)
Singh, Ashish Kumar
Fe-based amorphous alloys are gaining increasing attention due to their exceptional wear and corrosion resistance for potential structural applications. Two major challenges that are hindering the commercialization of these amorphous alloys are difficulty in processing of bulk shapes (diameter > 10 mm) and lack of ductility. Spark plasma sintering (SPS) is evolving as a promising technique for processing bulk shapes of amorphous and nanocrystalline materials. The objective of this work is to investigate densification behavior, nanocrystallization, and mechanical properties of SPS sintered Fe-based amorphous alloys of composition Fe48Cr15Mo14Y2C15B6. SPS processing was performed in three distinct temperature ranges of amorphous alloys: (a) below glass transition temperature (Tg), (b) between Tg and crystallization temperature (Tx), and (c) above Tx. Punch displacement data obtained during SPS sintering was correlated with the SPS processing parameters such as temperature, pressure, and sintering time. Powder rearrangement, plastic deformation below T g, and viscous flow of the material between Tg and Tx were observed as the main densification stages during SPS sintering. Micro-scale temperature distributions at the point of contact and macro-scale temperature distribution throughout the sample during SPS of amorphous alloys were modeled. The bulk amorphous alloys are expected to undergo structural relaxation and nanocrystallization during SPS sintering. X-ray diffraction (XRD), small angle neutron scattering (SANS), and transmission electron microscopy (TEM) was performed to investigate the evolution of nanocrystallites in SPS sintered Fe-based bulk amorphous alloys. The SANS analysis showed significant scattering for the samples sintered in the supercooled region indicating local structural and compositional changes with the profuse nucleation of nano-clusters (~4 nm). Compression tests and microhardness were performed on the samples sintered at different temperatures ranging from 570 °C to 800 °C. Maximum compression strength (1.1+/-0.2 MPa) was obtained for the samples sintered in the supercooled region. Effects of crystallization on tribological behavior of sintered samples were also investigated where crystallization resulted in increase in wear resistance. Laser surface hardening of SPS sintered amorphous samples were performed. Depending on the processing parameters, the laser surface irradiation causes structural relaxation and nanocrystallization, resulting in surface hardening.
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NASA Astrophysics Data System (ADS)
Zhang, Huiyan; Feng, Yuping; Nieto, Daniel; García-Lecina, Eva; Mcdaniel, Clare; Díaz-Marcos, Jordi; Flores-Arias, María Teresa; Gerard M., O.'connor; Baró, Maria Dolors; Pellicer, Eva; Sort, Jordi
2016-05-01
Periodic ripple and nanoripple patterns are formed at the surface of amorphous steel after femtosecond pulsed laser irradiation (FSPLI). Formation of such ripples is accompanied with the emergence of a surface ferromagnetic behavior which is not initially present in the non-irradiated amorphous steel. The occurrence of ferromagnetic properties is associated with the laser-induced devitrification of the glassy structure to form ferromagnetic (α-Fe and Fe3C) and ferrimagnetic [(Fe,Mn)3O4 and Fe2CrO4] phases located in the ripples. The generation of magnetic structures by FSPLI turns out to be one of the fastest ways to induce magnetic patterning without the need of any shadow mask. Furthermore, local variations of the adhesion force, wettability and nanomechanical properties are also observed and compared to those of the as-cast amorphous alloy. These effects are of interest for applications (e.g., biological, magnetic recording, etc.) where both ferromagnetism and tribological/adhesion properties act synergistically to optimize material performance.
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The nanophase iron mineral(s) in Mars soil
NASA Technical Reports Server (NTRS)
Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.
1993-01-01
A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.
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River-derived humic substances as iron chelators in seawater
Krachler, Regina; Krachler, Rudolf F.; Wallner, Gabriele; Hann, Stephan; Laux, Monika; Cervantes Recalde, Maria F.; Jirsa, Franz; Neubauer, Elisabeth; von der Kammer, Frank; Hofmann, Thilo; Keppler, Bernhard K.
2015-01-01
The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 μg L− 1. Terrigenous NOM concentrations ≥ 5 μg L− 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought. PMID:26412934
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NASA Astrophysics Data System (ADS)
Krishna, N. S.; Doko, N.; Matsuo, N.; Saito, H.; Yuasa, S.
2017-11-01
We have grown Fe(0 0 1)/GaO x (0 0 1)/MgO(0 0 1)/Fe(0 0 1) magnetic tunnel junctions (MTJs) with or without in situ annealing after the deposition of GaO x layer and performed structural characterizations by focusing on the formation process of the single-crystalline GaO x . It was found that, even without the in situ annealing, the as-grown GaO x grown on the MgO was mostly single-crystalline except near the surface region (amorphous). The crystallization temperature of the amorphous region was reduced from 500 °C down to 250 °C by depositing the Fe upper electrode (poly-crystalline). It was clarified that the crystallization of the amorphous region near the Fe/GaO x interface caused the realignments of the crystal grains in the poly-crystalline Fe upper electrode, and, as a result, the fully epitaxial Fe/GaO x /MgO/Fe structure is eventually formed. All the MTJs showed high tunneling magnetoresistance ratios (about 100%) at room temperature, which was almost independent of the formation temperature of the single-crystalline GaO x .
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NASA Astrophysics Data System (ADS)
Snyder, J. E.; Harris, V. G.; Koon, N. C.; Sui, X.; Kryder, M. H.
1996-10-01
Anisotropic local structure has been observed around both the Fe and Ba ions in the amorphous precursor to Ba-hexaferrite thin films, using polarization-dependent extended x-ray-absorption fine structure. This anisotropic local structure, consisting mainly of a network of Fe-O octahedra, determines the orientation of the fast-growing basal planes during crystallization, and thus the directions of the c axes and the resulting magnetic anisotropy.
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230% room-temperature magnetoresistance in CoFeB /MgO/CoFeB magnetic tunnel junctions
NASA Astrophysics Data System (ADS)
Djayaprawira, David D.; Tsunekawa, Koji; Nagai, Motonobu; Maehara, Hiroki; Yamagata, Shinji; Watanabe, Naoki; Yuasa, Shinji; Suzuki, Yoshishige; Ando, Koji
2005-02-01
Magnetoresistance (MR) ratio up to 230% at room temperature (294% at 20 K) has been observed in spin-valve-type magnetic tunnel junctions (MTJs) using MgO tunnel barrier layer fabricated on thermally oxidized Si substrates. We found that such a high MR ratio can be obtained when the MgO barrier layer was sandwiched with amorphous CoFeB ferromagnetic electrodes. Microstructure analysis revealed that the MgO layer with (001) fiber texture was realized when the MgO layer was grown on amorphous CoFeB rather than on polycrystalline CoFe. Since there have been no theoretical studies on the MTJs with a crystalline tunnel barrier and amorphous electrodes, the detailed mechanism of the huge tunneling MR effect observed in this study is not clear at the present stage. Nevertheless, the present work is of paramount importance in realizing high-density magnetoresistive random access memory and read head for ultra high-density hard-disk drives into practical use.
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Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li
2013-01-01
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.
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Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li
2013-01-01
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. PMID:24260377
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Reaction of amorphous/crystalline SiOC/Fe interfaces by thermal annealing
Su, Qing; Zhernenkov, Mikhail; Ding, Hepeng; ...
2017-06-12
The development of revolutionary new alloys and composites is crucial to meeting materials requirements for next generation nuclear reactors. The newly developed amorphous silicon oxycarbide (SiOC) and crystalline Fe composite system has shown radiation tolerance over a wide range of temperatures. To advance understanding of this new composite, we investigate the structure and thermal stability of the interface between amorphous SiOC and crystalline Fe by combining various experimental techniques and simulation methods. We show that the SiOC/Fe interface is thermally stable up to at least 400 °C. When the annealing temperature reaches 600 °C, an intermixed region forms at thismore » interface. This region appears to be a crystalline phase that forms an incoherent interface with the Fe layer. Density functional theory (DFT) Molecular dynamics (MD) is performed on the homogeneous SiFeOC phase to study the early stages of 2 formation of the intermixed layer. Both experimental and simulation results suggest this phase has the fayalite crystal structure. As a result, the physical processes involved in the formation of the intermixed region are discussed.« less
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Temperature-Dependent Helium Ion-Beam Mixing in an Amorphous SiOC/Crystalline Fe Composite
Su, Qing; Price, Lloyd; Shao, Lin; ...
2016-10-31
Temperature dependent He-irradiation-induced ion-beam mixing between amorphous silicon oxycarbide (SiOC) and crystalline Fe was examined with a transmission electron microscope (TEM) and via Rutherford backscattering spectrometry (RBS). The Fe marker layer (7.2 ± 0.8 nm) was placed in between two amorphous SiOC layers (200 nm). The amount of ion-beam mixing after 298, 473, 673, 873, and 1073 K irradiation was investigated. Both TEM and RBS results showed no ion-beam mixing between Fe and SiOC after 473 and 673 K irradiation and a very trivial amount of ion-beam mixing (~2 nm) after 298 K irradiation. At irradiation temperatures higher than 873more » K, the Fe marker layer broke down and RBS could no longer be used to quantitatively examine the amount of ion mixing. The results indicate that the Fe/SiOC nanocomposite is thermally stable and tends to demix in the temperature range from 473 to 673 K. For application of this composite structure at temperatures of 873 K or higher, layer stability is a key consideration.« less
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NASA Technical Reports Server (NTRS)
Bell, J. F., III; Roush, T. L.
1993-01-01
The research presented here represents the initial phase of a broader project that is intended to provide data in the mid- and far-IR spectral region for both well-characterized iron oxides/oxyhydroxides and poorly crystalline or amorphous materials (e.g., palagonites). Such information can be used in the interpretation of data to be returned by the Mars Observer Thermal Emission Spectrometer (TES). Additionally, this same information will prove useful for assessing the information content of existing Kuiper Airborne Observatory, Mariner 7, and Mariner 9 spectra. which also cover the thermal IR wavelength region.
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NASA Astrophysics Data System (ADS)
Coward, E.; Thompson, A.; Plante, A. F.
2014-12-01
The long residence time of soil organic matter (SOM) is a dynamic property, reflecting the diversity of stabilization mechanisms active within the soil matrix. Climate and ecosystem properties act at the broadest scale, while biochemical recalcitrance, physical occlusion and mineral association drive stability at the microscale. Increasing evidence suggests that the stability of SOM is dominated by organo-mineral interactions. However, the 2:1 clays that provide much of the stabilization capacity in temperate soils are typically absent in tropical soils due to weathering. In contrast, these soils may contain an abundance of iron and aluminium oxides and oxyhydroxides, known as short-range-order (SRO) minerals. These SRO minerals are capable of SOM stabilization through adsorption or co-precipitation, a faculty largely enabled by their high specific surface area (SSA). As such, despite their relatively small mass, SRO minerals may contribute substantially to the SOM stabilization capacity of tropical soils. The objective of this work is to characterize and quantify these Fe-C interactions. Surface (0-20 cm) soil samples were taken from 20 quantitative soil pits dug within the Luquillo Critical Zone Observatory in northeast Puerto Rico. Soils were stratified across granodiorite and volcaniclastic parent materials. Four extraction procedures were used to isolate three different forms of Fe-C interactions: sodium pyrophosphate to isolate organo-metallic complexes, hydroxylamine and oxalate to isolate SRO Fe- and Al-hydroxides, and dithionite to isolate crystalline Fe-oxyhydroxides. Extracts were analysed for DOC and Fe and Al concentrations to estimate the amount of SOM associated with each mineral type. Soils were subjected to SSA and solid-phase C analyses before and after extraction to determine the contribution of the various Fe mineral types to soil SSA, and therefore to potential stabilization capacity through organo-mineral complexation. Preliminary results suggest that extracts from granodiorite parent material contain on average twice the Fe than those from volcaniclastic parent material. The removal of SRO minerals reduced SSA in both soil types, and appear to contribute substantially to SOM stabilization compared to the bulk mineral matrix.
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Local Structure and Anisotropy in the Amorphous Precursor= to Ba-Hexaferrite Thin Films
NASA Astrophysics Data System (ADS)
Snyder, J. E.; Harris, V. G.; Koon, N. C.; Sui, X.; Kryder, M. H.
1996-03-01
Ba-hexaferrite thin-films for recording media applications are commonly fabricated by a two-step process: sputter-deposition of an amorphous precursor, followed by annealing to crystallize the BaFe_12O_19 phase. The magnetic anisotropy of the crystalline films can be either in-plane or perpendicular, depending on the sputtering process used in the first step. However, conventional characterization techniques (x-ray diffraction and TEM) have been unable to observe any structure in the amorphous precursor films. In this study, such films are investigated by PD-EXAFS (polarization-dependent extended x-ray absorption fine structure). An anisotropic local ordered structure is observed around both Fe and Ba atoms in the "amorphous" films. This anisotropic local structure appears to determine the orientation of the fast-growing basal plane directions during crystallization, and thus the directions of the c-axes and the magnetic anisotropy. Results suggest that the structure of the amorphous films consists of networks made up of units of Fe atoms surrounded by their O nearest neighbors, that are connected together. Ba atoms appear to fit into in-between spaces as network-modifiers.
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Electrodeposition of amorphous Ni P coatings onto Nd Fe B permanent magnet substrates
NASA Astrophysics Data System (ADS)
Ma, C. B.; Cao, F. H.; Zhang, Z.; Zhang, J. Q.
2006-12-01
Decorative and protective Ni-P amorphous coatings were electroplated onto NdFeB permanent magnet from an ortho-phosphorous acid contained bath. The influences of the main electroplating technological parameters including current density, bath pH, bath temperature and H3PO3 on the structure and chemical composition of Ni-P coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques in conjunction with X-ray diffraction (XRD), scanning transmission electron microscopy (SEM) and X-ray energy-dispersive spectrometry (EDX). The optimized amorphous Ni-P coated NdFeB can stand for ca. 180 h against neutral 3.0 wt.% NaCl salt spray without any pitting corrosion. Meanwhile, the results also showed that large phosphorous content is the precondition for Ni-P coatings to possess the amorphous structure, but too much high phosphorous content can damage the amorphous structure due to the separation of superfluous P from Ni2P/Ni3P and the resultant formation of multi-phase coatings (such as Ni2P-P).
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RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation
NASA Astrophysics Data System (ADS)
Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng
2018-04-01
Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.
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Natural attenuation of arsenic in the environment by immobilization in nanostructured hematite.
Freitas, Erico T F; Montoro, Luciano A; Gasparon, Massimo; Ciminelli, Virginia S T
2015-11-01
Iron (hydr)oxides are known to play a major role in arsenic fixation in the environment. The mechanisms for long-term fixation into their crystal structure, however, remain poorly understood, especially arsenic partitioning behavior during transformation from amorphous to crystalline phases under natural conditions. In this study, these mechanisms are investigated in Fe-Al-oxisols exposed over a period of 10 years to a sulfide concentrate in tailings impoundments. The spatial resolution necessary to investigate the markedly heterogeneous nanoscale phases found in the oxisols was achieved by combining three different, high resolution electron microscopy techniques - Nano-Beam Electron Diffraction (NBD), Electron Energy-Loss Spectroscopy (EELS), and High Resolution Transmission Electron Microscopy (HRTEM). Arsenic (1.6±0.5 wt.%) was unambiguously and precisely identified in mesocrystals of Al-hematite with an As/Fe atomic ratio of 0.026±0.006. The increase in the c-axis (c=1.379±0.009 nm) compared to standard hematite (c=1.372 nm) is consistent with the presence of arsenic in the Al-hematite structure. The As-bearing Al-hematite is interpreted as a secondary phase formed from oxyhydroxides, such as ferrihydrite, during the long-term exposure to the sulfide tailings. The proposed mechanism of arsenic fixation in the Al-hematite structure involves adsorption onto Al-ferrihydrite nanoparticles, followed by Al-ferrihydrite aggregation by self-assembly oriented attachment and coalescence that ultimately produces Al-hematite mesocrystals. Our results illustrate for the first time the process of formation of stable arsenic bearing Al-hematite for the long-term immobilization of arsenic in environmental samples. Copyright © 2015 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Koukina, S. E.; Lobus, N. V.; Peresypkin, V. I.; Dara, O. M.; Smurov, A. V.
2017-11-01
Major (Si, Al, Fe, Ti, Mg, Ca, Na, K, S, P), minor (Mn) and trace (Li, V, Cr, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Cd, Ag, Sn, Sb, Cs, Ba, Hg, Pb, Bi and U) elements, their chemical forms and the mineral composition, organic matter (TOC) and carbonates (TIC) in surface sediments from the Cai River estuary and Nha Trang Bay were first determined along the salinity gradient. The abundance and ratio of major and trace elements in surface sediments are discussed in relation to the mineralogy, grain size, depositional conditions, reference background and SQG values. Most trace-element contents are at natural levels and are derived from the composition of rocks and soils in the watershed. A severe enrichment of Ag is most likely derived from metal-rich detrital heavy minerals such as Ag-sulfosalts. Along the salinity gradient, several zones of metal enrichment occur in surface sediments because of the geochemical fractionation of the riverine material. The parts of actually and potentially bioavailable forms (isolated by four single chemical reagent extractions) are most elevated for Mn and Pb (up to 36% and 32% of total content, respectively). The possible anthropogenic input of Pb in the region requires further study. Overall, the most bioavailable parts of trace elements are associated with easily soluble amorphous Fe and Mn oxyhydroxides. The sediments are primarily enriched with bioavailable metal forms in the riverine part of the estuary. Natural (such as turbidities) and human-generated (such as urban and industrial activities) pressures are shown to influence the abundance and speciation of potential contaminants and therefore change their bioavailability in this estuarine system.
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Fernández Barquín, L; Yedra Martínez, A; Rodríguez Fernández, L; Rojas, D P; Murphy, F J; Alba Venero, D; Ruiz González, L; González-Calbet, J; Fdez-Gubieda, M L; Pankhurst, Q A
2012-03-01
The structural and magnetic properties of a collection of nanoparticles coated by Poly(methyl methacrylate) through a wet chemical synthesis have been investigated. The particles display either an amorphous (M = Fe, Co) M-B arrangement or a mixed structure bcc-Fe and fcc-Co + amorphous M-B. Both show the presence of a metal oxi-hydroxide formed in aqueous reduction. The organic coating facilitates technological handling. The cost-effective synthesis involves a reduction in a Poly(methyl methacrylate) aqueous solution of iron(II) or cobalt(II) sulphates (< 0.5 M) by sodium borohydride (< 0.5 M). The particles present an oxidized component, as deduced from X-ray diffraction, Mössbauer and Fe- and Co K-edge X-ray absorption spectroscopy and electron microscopy. For the ferrous alloys, this Fe-oxide is alpha-goethite, favoured by the aqueous solution. The Poly(methyl methacrylate) coating is confirmed by Fourier transform infrared spectroscopy. In pure amorphous core alloys there is a drastic change of the coercivity from bulk to around 30 Oe in the nanoparticles. The mixed structured alloys also lie in the soft magnetic regime. Magnetisation values at room temperature range around 100 emu/g. The coercivity stems from multidomain particles and their agglomeration, triggering the dipolar interactions.
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Arsenic in rice agrosystems (water, soil and rice plants) in Guayas and Los Ríos provinces, Ecuador.
Otero, X L; Tierra, W; Atiaga, O; Guanoluisa, D; Nunes, L M; Ferreira, T O; Ruales, J
2016-12-15
Geogenic arsenic (As) can accumulate and reach high concentrations in rice grains, thus representing a potential threat to human health. Ecuador is one of the main consumers of rice in South America. However, there is no information available about the concentrations of As in rice agrosystems, although some water bodies are known to contain high levels of the element. We carried out extensive sampling of water, soil, rice plants and commercial rice (obtained from local markets). Water samples were analysed to determine physico-chemical properties and concentrations of dissolved arsenic. Soil samples were analysed to determine total organic C, texture, total Fe and amorphous Fe oxyhydroxides (Fe Ox ), total arsenic (tAs) and the bioavailable fraction (As Me ). The different plant parts were analysed separately to determine total (tAs), inorganic (iAs) and organic arsenic (oAs). Low concentrations of arsenic were found in samples of water (generally <10μgl -1 ) and soil (4.48±3mgkg -1 ). The tAs in the rice grains was within the usual range (0.042-0.125mgkg -1 dry weight, d.w.) and was significantly lower than in leaves (0.123-0.286mgkg -1 d.w.) and stems (0.091-0.201mgkg -1 d.w.). The Fe Ox and tAs and also As Me in flood water were negatively correlated with tAs in the plants. However, the concentrations of As in stems and leaves were linearly correlated with tAs in the soil and flood water. The relationship between tAs and arsenic in the grain fitted a logarithmic function, as did that between tAs in the grain and the stem. The findings seem to indicate that high concentrations of arsenic in the environment (soil or water) or in the rice stem do not necessarily imply accumulation of the element in the grain. The iAs form was dominant (>80%) in all parts of the rice plants. Copyright © 2016 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Brodie, E. L.; Beller, H. R.; Goldfarb, K. C.; Han, R.; Santee, C. A.
2009-12-01
In situ reductive immobilization, whereby highly soluble Cr(VI) species are reduced to poorly soluble Cr(III) species, is a favored approach for remediating Cr-contaminated groundwater. How microbial populations respond phylogenetically and functionally to the injection of an organic electron donor to stimulate Cr(VI) reduction is unclear, as are the relative contributions of direct enzymatic Cr(VI) reduction versus indirect (e.g. sulfide-mediated) reduction. In this study, we inoculated anaerobic microcosms with groundwater from the Cr-contaminated Hanford 100H site (WA) and supplemented them with lactate and the electron acceptors nitrate, sulfate, and amorphous ferric oxyhydroxide. The microcosms progressed successively through nitrate-reducing, sulfate-reducing, and Fe(III)-reducing conditions, and after a second nitrate amendment, nitrate-dependent Fe(II)-oxidizing conditions. Cr(VI) reduction occurred during both the denitrification and the sulfate/iron reduction phases. DNA and RNA were harvested during each major biogeochemical phase and were subjected to PhyloChip analysis, qPCR, and transcript sequencing. Bacterial community succession followed a trajectory related to the sequential use of electron acceptors. During denitrification, bacterial communities were enriched in known denitrifiers within the Beta- and Gamma-proteobacteria and became phylogenetically clustered. Fermenters became enriched following nitrate reduction, preceding both iron and sulfate reduction. Iron reduction was stoichiometrically related to the formation of hydrogen sulfide and, although iron reducers were detected during this phase, their iron-reducing activity was not confirmed. Following the depletion of lactate and sulfate, iron reduction rates decreased and acetate and propionate concentrations stabilized, indicating a marginal contribution of acetate-coupled iron reduction. Rapid Fe(II) oxidation occurred following the nitrate amendment with a concomitant reduction of nitrate to nitrite and an increased abundance of Beta-proteobacterial species related to known anaerobic Fe(II)-oxidizing bacteria. To uncover the microbial mechanisms contributing to the biogeochemical complexity encountered, even under controlled laboratory incubations, requires alternatives to standard phylogenetic analyses. Our ongoing efforts in analyzing the community transcriptomes (mRNA) should provide valuable insight into the relative rates of direct versus indirect mechanisms of Cr(VI) immobilization in contaminated aquifers.
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Ultra-high power capabilities in amorphous FePO4 thin films
NASA Astrophysics Data System (ADS)
Gandrud, Knut B.; Nilsen, Ola; Fjellvåg, Helmer
2016-02-01
Record breaking electrochemical properties of FePO4 have been found through investigation of the thickness dependent electrochemical properties of amorphous thin film electrodes. Atomic layer deposition was used for production of thin films of amorphous FePO4 with highly accurate thickness and topography. Electrochemical characterization of these thin film electrodes revealed that the thinner electrodes behave in a pseudocapacitive manner even at high rates of Li+ de/intercalation, which enabled specific powers above 1 MW kg-1 FePO4 to be obtained with minimal capacity loss. In addition, a self-enhancing kinetic effect was observed during cycling enabling more than 10,000 cycles at current rates approaching that of a supercapacitor (11s charge/discharge). The current findings may open for construction of ultra-high power battery electrodes that combines the energy density of batteries with the power capabilities of supercapacitors.
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Anaerobic methanotrophy in tidal wetland: Effects of electron acceptors
NASA Astrophysics Data System (ADS)
Lin, Li-Hung; Yu, Zih-Huei; Wang, Pei-Ling
2016-04-01
Wetlands have been considered to represent the largest natural source of methane emission, contributing substantially to intensify greenhouse effect. Despite in situ methanogenesis fueled by organic degradation, methanotrophy also plays a vital role in controlling the exact quantity of methane release across the air-sediment interface. As wetlands constantly experience various disturbances of anthropogenic activities, biological burrowing, tidal inundation, and plant development, rapid elemental turnover would enable various electron acceptors available for anaerobic methanotrophy. The effects of electron acceptors on stimulating anaerobic methanotrophy and the population compositions involved in carbon transformation in wetland sediments are poorly explored. In this study, sediments recovered from tidally influenced, mangrove covered wetland in northern Taiwan were incubated under the static conditions to investigate whether anaerobic methanotrophy could be stimulated by the presence of individual electron acceptors. Our results demonstrated that anaerobic methanotrophy was clearly stimulated in incubations amended with no electron acceptor, sulfate, or Fe-oxyhydroxide. No apparent methane consumption was observed in incubations with nitrate, citrate, fumarate or Mn-oxides. Anaerobic methanotrophy in incubations with no exogenous electron acceptor appears to proceed at the greatest rates, being sequentially followed by incubations with sulfate and Fe-oxyhydroxide. The presence of basal salt solution stimulated methane oxidation by a factor of 2 to 3. In addition to the direct impact of electron acceptor and basal salts, incubations with sediments retrieved from low tide period yielded a lower rate of methane oxidation than from high tide period. Overall, this study demonstrates that anaerobic methanotrophy in wetland sediments could proceed under various treatments of electron acceptors. Low sulfate content is not a critical factor in inhibiting methane consumption, suggesting that unlike the consensus derived from marine sediments, anaerobic methanotrophy might not be necessarily coupled with sulfate reduction. The regeneration of Fe-oxyhydroxide during cyclic tidal recession provides an alternative pathway to maintain methanotrophic activity. The ultimate control on methane oxidation and emission is, however, complicated by the interplay between oxygen penetration, organotrophic sulfate reduction, methanogenesis, methanotrophy, and anaerobic sulfate production modulated by tidal influence.
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Roulet, M; Lucotte, M; Saint-Aubin, A; Tran, S; Rhéault, I; Farella, N; De Jesus Da silva, E; Dezencourt, J; Sousa Passos, C J; Santos Soares, G; Guimarães, J R; Mergler, D; Amorim, M
1998-11-03
In an oxisol-spodosol system developed on the terrestrial surface of the lower Tapajós Valley, the determination of total mercury (Hg), organic carbon (C), iron and aluminum oxy-hydroxide (Fe(cdb) and Al(cdb)) concentrations in the surface soil horizons are used to characterise the geochemical processes controlling the accumulation of Hg in soils under natural vegetation cover and in deforested and cultivated sites. Oxisols from the plateau have homogeneous and relatively high background Hg contents and burdens constituting an important natural reservoir of Hg for the region (90-210 ng/g dry wt. and 19-33 mg/m2 for the first 20 cm). The Fe(cdb) and Al(cdb) contents associated with the fine fraction (< 63 microns) of the soil suggest that oxy-hydroxides and, particularly Al-substituted Fe oxy-hydroxides, control the Hg concentrations observed in all of the soils of the study region. Consequently, the geochemistry of these minerals along the slopes governs the accumulation or the release of the Hg according to the natural evolution of the soil cover and/or following the degradation of soils by erosion after deforestation and cultivation. These observations have important implications for the interpretation of Hg contamination patterns observed in Amazonian aquatic systems that could be linked to different drainage sources of Hg from the terrestrial surface. The sandification and podzolisation that is characteristic of the evolution of numerous pedological systems in the equatorial Amazon could be responsible for exportation of the naturally accumulated Hg, as for other metals, by acidic complexation and migration to the black waters of the Amazon. In the central Amazon region, as a result of the fragility of the soil cover, deforestation and cultivation, affecting principally the superficial soil, promote the selective erosion of fine particles enriched in oxides and Hg. The erosion of soil could be responsible for an important release of Hg, transported in particulate form by drainage waters.
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Microbial exudate promoted dissolution and transformation of chromium containing minerals
NASA Astrophysics Data System (ADS)
Saad, E. M.; Sun, J.; Tang, Y.
2015-12-01
Because of its utility in many industrial processes, chromium has become the second most common metal contaminant in the United States. The two most common oxidation states of chromium in nature are Cr(III), which is highly immobile, and Cr(VI), which is highly mobile and toxic. In both natural and engineered environments, the most common remediation of Cr(VI) is through reduction, which results in chromium sequestration in the low solubility mixed Cr(III)-Fe(III) (oxy)hydroxide phases. Consequently, the stability of these minerals must be examined to assess the fate of chromium in the subsurface. We examined the dissolution of mixed Cr(III)-Fe(III) (oxy)hydroxides in the presence of common microbial exudates, including the siderophore desferrioxamine B (DFOB; a common organic ligand secreted by most microbes with high affinity for ferric iron and other trivalent metal ions) and oxalate (a common organic acid produced by microbes). The solids exhibited incongruent dissolution with preferential leaching of Fe from the solid phase. Over time, this leads to a more Cr rich mineral, which is known to be more soluble than the corresponding mixed mineral phase. We are currently investigating the structure of the reacted mineral phases and soluble Cr(III) species, as well as the potential oxidation and remobilization of the soluble Cr species. Results from this study will provide insights regarding the long term transport and fate of chromium in the natural environment in the presence of microbial activities.
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Ren, Xiang; Wang, Weiyi; Ge, Ruixiang; Hao, Shuai; Qu, Fengli; Du, Gu; Asiri, Abdullah M; Wei, Qin; Chen, Liang; Sun, Xuping
2017-08-08
It is highly attractive to develop efficient hydrogen-evolving electrocatalysts under neutral conditions. In this communication, we report an amorphous FeMoS 4 nanorod array on carbon cloth (FeMoS 4 NRA/CC) prepared by hydrothermal treatment of an FeOOH nanorod array on carbon cloth (FeOOH NRA/CC) in (NH 4 ) 2 MoS 4 solution. As a 3D electrode for hydrogen evolution electrocatalysis, this FeMoS 4 NRA/CC demonstrates superior catalytic activity and strong long-term electrochemical durability in 1.0 M phosphate buffered saline (pH: 7). It needs an overpotential of 204 mV to drive a geometrical current density of 10 mA cm -2 , which is 450 mV less than that for FeOOH NRA/CC. Density functional theory calculations suggest that FeMoS 4 has a more favourable hydrogen adsorption free energy than FeOOH.
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NASA Astrophysics Data System (ADS)
Horneman, A.; van Geen, A.; Kent, D. V.; Mathe, P. E.; Zheng, Y.; Dhar, R. K.; O'Connell, S.; Hoque, M. A.; Aziz, Z.; Shamsudduha, M.; Seddique, A. A.; Ahmed, K. M.
2004-09-01
This study reexamines the notion that extensive As mobilization in anoxic groundwater of Bangladesh is intimately linked to the dissolution of Fe oxyhydroxides on the basis of analyses performed on a suite of freshly collected samples of aquifer material. Detailed sediment profiles extending to 40 to 70 m depth below the surface were obtained at six sites where local groundwater As concentrations were known to span a wide range. The sediment properties that were measured include (1) the proportion of Fe(II) in the Fe fraction leached in hot 1.2 N HCl, (2) diffuse spectral reflectance, and (3) magnetic susceptibility. In parallel with local concentrations of dissolved As ranging from <5 to 600 μg/L, Fe(II)/Fe ratios in shallow (gray) Holocene sands tended to gradually increase with depth from values of 0.3 to 0.5 to up to 0.9. In deeper (orange) aquifers of presumed Pleistocene age that were separated from shallow sands by a clay layer and contained <5 μg/L dissolved As, leachable Fe(II)/Fe ratios averaged ˜0.2. There was no consistent relation between sediment Fe(II)/Fe and dissolved Fe concentrations in groundwater in nearby wells. The reflectance measurements indicate a systematic linear relation (R 2 of 0.66; n = 151) between the first derivative transform of the reflectance at 520 nm and Fe(II)/Fe. The magnetic susceptibility of the shallow aquifer sands ranged from 200 to 3600 (x 10 -9 m 3/kg SI) and was linearly related (R 2 of 0.75; n = 29) to the concentrations of minerals that could be magnetically separated (0.03 to 0.79% dry weight). No systematic depth trends in magnetic susceptibility were observed within the shallow sands, although the susceptibility of deeper low-As aquifers was low (up to ˜200 × 10 -9 m 3/kg SI). This set of observations, complemented by incubation results described in a companion paper by van Geen et al. (this volume), suggests that the release of As is linked to the transformation of predominantly Fe (III) oxyhydroxide coatings on sand particles to Fe(II) or mixed Fe(II/III) solid phases with a flatter reflectance spectrum such as siderite, vivianite, or magnetite, without necessarily resulting in the release of Fe to groundwater. The very low As/Fe ratio of magnetically separated minerals compared to the As/Fe of bulk acid leachate (2 vs. 40 10 -6, respectively) suggests that such a transformation could be accompanied by a significant redistribution of As to a mobilizable phase on the surface of aquifer particles.
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Fe-Based Amorphous Coatings on AISI 4130 Structural Steel for Corrosion Resistance
NASA Astrophysics Data System (ADS)
Katakam, Shravana; Santhanakrishnan, S.; Dahotre, Narendra B.
2012-06-01
The current study focuses on synthesizing a novel functional coating for corrosion resistance applications, via laser surface alloying. The iron-based (Fe48Cr15Mo14Y2C15B) amorphous precursor powder is used for laser surface alloying on AISI 4130 steel substrate, with a continuous wave ytterbium Nd-YAG fiber laser. The corrosion resistance of the coatings is evaluated for different processing conditions. The microstructural evolution and the response of the microstructure to the corrosive environment is studied using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Microstructural studies indicate the presence of face-centered cubic Fe-based dendrites intermixed within an amorphous matrix along with fine crystalline precipitates. The corrosion resistance of the coatings decrease with an increase in laser energy density, which is attributed to the precipitation and growth of chromium carbide. The enhanced corrosion resistance of the coatings processed with low energy density is attributed to the self-healing mechanism of this amorphous system.
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Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China.
Bu, Hongmei; Song, Xianfang; Guo, Fen
2017-01-15
Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.
2009-01-01
The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced flux of Fe-Mn oxide removal as a result of increased biological uptake of Fe and Mn. ?? 2008 Elsevier B.V. All rights reserved.
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CFA Films in Amorphous Substrate: Structural Phase Induction and Magnetization Dynamics
NASA Astrophysics Data System (ADS)
Correa, M. A.; Bohn, F.; Escobar, V. M.
We report a systematic study of the structural and quasi-static magnetic properties, as well as of the dynamic magnetic response through MI effect, in Co2FeAl and MgO//Co2FeAl single layers and a MgO//Co2FeAl/Ag/Co2FeAl trilayered film, all grown onto an amorphous substrate. We present a new route to induce the crystalline structure in the Co2FeAl alloy and verify that changes in the structural phase of this material leads to remarkable modifications of the magnetic anisotropy and, consequently, dynamic magnetic behavior. Considering the electrical and magnetic properties of the Co2FeAl, our results open new possibilities for technological applications of this full-Heusler alloy in rigid and flexible spintronic devices.
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The effect of initial pressure on growth of FeNPs in amorphous carbon films
NASA Astrophysics Data System (ADS)
Mashayekhi, Fatemeh; Shafiekhani, Azizollah; Sebt, S. Ali; Darabi, Elham
2018-04-01
Iron nanoparticles in amorphous hydrogenated carbon films (FeNPs@a-C:H) were prepared with RF-sputtering and RFPECVD methods by acetylene gas and Fe target. In this paper, deposition and sputtering process were carried out under influence of different initial pressure gas. The morphology and roughness of surface of samples were studied by AFM technique and also TEM images show the exact size of FeNPs and encapsulated FeNPs@a-C:H. The localized surface plasmon resonance peak (LSPR) of FeNPs was studied using UV-vis absorption spectrum. The results show that the intensity and position of LSPR peak are increased by increasing initial pressure. Also, direct energy gap of samples obtained by Tauc law is decreased with respect to increasing initial pressure.
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Si-FeSi2/C nanocomposite anode materials produced by two-stage high-energy mechanical milling
NASA Astrophysics Data System (ADS)
Yang, Yun Mo; Loka, Chadrasekhar; Kim, Dong Phil; Joo, Sin Yong; Moon, Sung Whan; Choi, Yi Sik; Park, Jung Han; Lee, Kee-Sun
2017-05-01
High capacity retention Silicon-based nanocomposite anode materials have been extensively explored for use in lithium-ion rechargeable batteries. Here we report the preparation of Si-FeSi2/C nanocomposite through scalable a two-stage high-energy mechanical milling process, in which nano-scale Si-FeSi2 powders are besieged by the carbon (graphite/amorphous phase) layer; and investigation of their structure, morphology and electrochemical performance. Raman analysis revealed that the carbon layer structure comprised of graphitic and amorphous phase rather than a single amorphous phase. Anodes fabricated with the Si-FeSi2/C showed excellent electrochemical behavior such as a first discharge capacity of 1082 mAh g-1 and a high capacity retention until the 30th cycle. A remarkable coulombic efficiency of 99.5% was achieved within a few cycles. Differential capacity plots of the Si-FeSi2/C anodes revealed a stable lithium reaction with Si for lithiation/delithiation. The enhanced electrochemical properties of the Si-FeSi2/C nanocomposite are mainly attributed to the nano-size Si and stable solid electrolyte interface formation and highly conductive path driven by the carbon layer.
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Magnetism from Fe2O3 nanoparticles embedded in amorphous SiO2 matrix
NASA Astrophysics Data System (ADS)
Sendil Kumar, A.; Bhatnagar, Anil K.
2018-02-01
Fe2O3 nanoparticles are embedded in amorphous SiO2 matrix by coprecipitation method with varying concentrations. Conditions are optimized to get almost monodispersed Fe2O3 nanoparticles with high chemical stability. Microstructure of synthesized nanoparticles is well characterized and found that Fe2O3 is in nanocrystalline form and embedded uniformly in amorphous SiO2 matrix. Enhanced surface reactivity is found for nanoparticles which influences physical properties of the SiO2 supported Fe2O3 system due to adsorption. In oxide nanoparticles, significant number of defect sites at the surface is expected but when supported medium such as SiO2 it reduces this defect concentration. Field- and temperature-dependent magnetisation studies on these samples show superparamagnetic behaviour. Superparamagnetic behaviour is seen in all the concentration systems but the coercivity observed in the lower concentration systems is found to be anomalous compared to that of higher concentrations. The observed magnetic behaviour comes from either unsaturated bond existing due to the absence of anions at the surface of nanoparticles or reconstruction of atomic orbitals taking place at interface of Fe2O3-SiO2 system.
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Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...
2015-10-22
Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less
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Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Perez Gonzalez, Teresa; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien
2013-09-10
The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.
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Homogeneously dispersed multimetal oxygen-evolving catalysts.
Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; Comin, Riccardo; Bajdich, Michal; García-Melchor, Max; Han, Lili; Xu, Jixian; Liu, Min; Zheng, Lirong; García de Arquer, F Pelayo; Dinh, Cao Thang; Fan, Fengjia; Yuan, Mingjian; Yassitepe, Emre; Chen, Ning; Regier, Tom; Liu, Pengfei; Li, Yuhang; De Luna, Phil; Janmohamed, Alyf; Xin, Huolin L; Yang, Huagui; Vojvodic, Aleksandra; Sargent, Edward H
2016-04-15
Earth-abundant first-row (3d) transition metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous metal distribution. These gelled FeCoW oxyhydroxides exhibit the lowest overpotential (191 millivolts) reported at 10 milliamperes per square centimeter in alkaline electrolyte. The catalyst shows no evidence of degradation after more than 500 hours of operation. X-ray absorption and computational studies reveal a synergistic interplay between tungsten, iron, and cobalt in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER. Copyright © 2016, American Association for the Advancement of Science.
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1983-08-19
Wang : CORROSION RESISTANCE OF AMORPHOUS AND CRYSTALLIZED Fe-Ni-Cr-W ALLOYS " 12:25 am M4 A. Yokoyama, H. Komiyama, H. Inoue, T. Masunoto, and H.M. Kimura...ENTHALPY RELAXATION IN PdNi ALLOY GLASSES 2:30 pm N3 A.I. Taub and J.L. Walter: SCALING THE COMPOSITION DEPENDENCE OF ATOMIC TRANSPORT AND STRUCTURAL...Cnn, L.Q. Wang , Y. Obi, and K. Fukamichi: LOW- TEMPERATURE SPECIFIC HEAT OF Fe-Zr AND Ni-Zr AMORPHOUS ALLOYS 2:15 pm 02 S.J. Poon: FLUX FLOW RESISTIVITY
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Moradi, M; Li, Z; Qi, JF
In this work we investigated an energy-efficient biotemplated route to synthesize nanostructured FePO4 for sodium-based batteries. Self-assembled M13 viruses and single wall carbon nanotubes (SWCNTs) have been used as a template to grow amorphous FePO4 nanoparticles at room temperature (the active composite is denoted as Bio-FePO4-CNT) to enhance the electronic conductivity of the active material. Preliminary tests demonstrate a discharge capacity as high as 166 mAh/g at C/10 rate, corresponding to composition Na0.9FePO4, which along with higher C-rate tests show this material to have the highest capacity and power performance reported for amorphous FePO4 electrodes to date.
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Hein, J.R.; Koski, R.A.; Embley, R.W.; Reid, J.; Chang, S.-W.
1999-01-01
This is the first reported occurrence of an active hydrothermal field in an oceanic fracture zone setting. The hydrothermal field occurs in a pull-apart basin within the Blanco Fracture Zone (BFZ), which has four distinct mineral deposit types: (1) barite mounds and chimneys, (2) barite stockwork breccia, (3) silica-barite beds, and (4) silica, barite, and Fe-Mn oxyhydroxide in sediments. All deposit types contain minor amounts of sulfides. In barite stockwork, silica-barite beds, and mineralized sediment, Ba, Ph, Ag, S, Au, Zn, Cu, Hg, TI, As, Mo, Sb, U, Cd, and Cu are enriched relative to unmineralized rocks and sediments of the BFZ. Fe and Mn are not enriched in the barite stockwork or silica-barite beds, but along with P, Co, and Mg are enriched in the mineralized sediments. Silver contents in deposits of the hydrothermal field range up to 86 ppm, gold to 0.7 ppm, zinc to 3.2%, copper to 0.8%, and barium to 22%. Mineralization occurred by diffuse, low to intermediate temperature (mostly <250??C) discharge of hydrothermal fluids through pillow lavas and ponds of mixed volcaniclastic and biosiliceous sediments. Bacterial mats were mineralized by silica, barite, and minor Fe hydroxides, or less commonly, by Mn oxyhydroxides. Pervasive mineralization of bacterial mats resulted in formation of silica-barite beds. Silica precipitated from hydrothermal fluids by conductive cooling and mixing with seawater. Sulfate, U, and rare earth elements (REEs) in barite were derived from seawater, whereas the REE content of hydrothermal silica deposits and mineralized sediments is associated with the aluminosilicate detrital fraction. Fe-, Zn-, Cu-, Pb-, and Hg-sulfide minerals, Ba in barite, and Eu in all mineralized deposits were derived from hydrothermal fluids. Manganese oxides and associated elements (Co, Sb, Mo, W, Cl, and Cu) and Fe oxides and associated elements (Be, B, P, and Mo) precipitated as the result of mixing of hydrothermal fluids with seawater. ?? 2001 Canadian Institute of Mining, Metallurgy and Petroleum. All rights reserved.
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Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.; ...
2017-05-19
Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Nicholas, Sarah L.; Erickson, Melinda L.; Woodruff, Laurel G.
Arsenic (As) is a geogenic contaminant affecting groundwater in geologically diverse systems globally. Arsenic release from aquifer sediments to groundwater is favored when biogeochemical conditions, especially oxidation-reduction (redox) potential, in aquifers fluctuate. The specific objective of this research is to identify the solid-phase sources and geochemical mechanisms of release of As in aquifers of the Des Moines Lobe glacial advance. The overarching concept is that conditions present at the aquifer-aquitard interfaces promote a suite of geochemical reactions leading to mineral alteration and release of As to groundwater. A microprobe X-ray absorption spectroscopy (μXAS) approach is developed and applied to rotosonicmore » drill core samples to identify the solid-phase speciation of As in aquifer, aquitard, and aquifer-aquitard interface sediments. This approach addresses the low solid-phase As concentrations, as well as the fine-scale physical and chemical heterogeneity of the sediments. The spectroscopy data are analyzed using novel cosine-distance and correlation-distance hierarchical clustering for Fe 1s and As 1s μXAS datasets. The solid-phase Fe and As speciation is then interpreted using sediment and well-water chemical data to propose solid-phase As reservoirs and release mechanisms. The results confirm that in two of the three locations studied, the glacial sediment forming the aquitard is the source of As to the aquifer sediments. The results are consistent with three different As release mechanisms: (1) desorption from Fe (oxyhydr)oxides, (2) reductive dissolution of Fe (oxyhydr)oxides, and (3) oxidative dissolution of Fe sulfides. The findings confirm that glacial sediments at the interface between aquifer and aquitard are geochemically active zones for As. The diversity of As release mechanisms is consistent with the geographic heterogeneity seen in the distribution of elevated-As wells.« less
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NASA Technical Reports Server (NTRS)
Bell, James F., III; Roush, Ted L.; Morris, Richard V.
1995-01-01
Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review existing data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestrial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+)-O(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.
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NASA Technical Reports Server (NTRS)
Bell, James F., III; Roush, Ted L.; Morris, Richard V.
1995-01-01
Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review exisiting data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+) - 0(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.
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Karamani, Anna A; Douvalis, Alexios P; Stalikas, Constantine D
2013-01-04
A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe(0)/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications. Copyright © 2012 Elsevier B.V. All rights reserved.
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Iron persistence in a distal hydrothermal plume supported by dissolved-particulate exchange
NASA Astrophysics Data System (ADS)
Fitzsimmons, Jessica N.; John, Seth G.; Marsay, Christopher M.; Hoffman, Colleen L.; Nicholas, Sarah L.; Toner, Brandy M.; German, Christopher R.; Sherrell, Robert M.
2017-02-01
Hydrothermally sourced dissolved metals have been recorded in all ocean basins. In the oceans' largest known hydrothermal plume, extending westwards across the Pacific from the Southern East Pacific Rise, dissolved iron and manganese were shown by the GEOTRACES program to be transported halfway across the Pacific. Here, we report that particulate iron and manganese in the same plume also exceed background concentrations, even 4,000 km from the vent source. Both dissolved and particulate iron deepen by more than 350 m relative to 3He--a non-reactive tracer of hydrothermal input--crossing isopycnals. Manganese shows no similar descent. Individual plume particle analyses indicate that particulate iron occurs within low-density organic matrices, consistent with its slow sinking rate of 5-10 m yr-1. Chemical speciation and isotopic composition analyses reveal that particulate iron consists of Fe(III) oxyhydroxides, whereas dissolved iron consists of nanoparticulate Fe(III) oxyhydroxides and an organically complexed iron phase. The descent of plume-dissolved iron is best explained by reversible exchange onto slowly sinking particles, probably mediated by organic compounds binding iron. We suggest that in ocean regimes with high particulate iron loadings, dissolved iron fluxes may depend on the balance between stabilization in the dissolved phase and the reversibility of exchange onto sinking particles.
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Antiferromagnetism in pressure-amorphized Fe2SiO4
Kruger, M.B.; Jeanloz, R.; Pasternak, M.P.; Taylor, R.D.; Snyder, B.S.; Stacy, A.M.; Bohlen, S.R.
1992-01-01
Amorphous Fe2SiO4 synthesized at elevated pressures exhibits a Ne??el transition at a temperature identical to that observed in the crystalline form, TN = 65 (??2) kelvin at zero pressure. This behavior contrasts sharply with observations on other disordered systems, such as spin glasses, which characteristically exhibit strong "frustration" of the spins and consequent marked suppression of the Ne??el transition.
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Chubar, Natalia; Gerda, Vasyl; Szlachta, Małgorzata
2014-11-18
Selenium cycling in the environment is greatly controlled by various minerals, including Mn and Fe hydrous oxides. At the same time, such hydrous oxides are the main inorganic ion exchangers suitable (on the basis of their chemical nature) to sorb (toxic) anions, separating them from water solutions. The mechanism of selenite adsorption by the new mixed adsorbent composed of a few (amorphous and crystalline) phases [maghemite, MnCO3, and X-ray amorphous Fe(III) and Mn(III) hydrous oxides] was studied by extended X-ray absorption fine structure (EXAFS) spectroscopy [supported by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data]. The complexity of the porous adsorbent, especially the presence of the amorphous phases of Fe(III) and Mn(III) hydrous oxides, is the main reason for its high selenite removal performance demonstrated by batch and column adsorption studies shown in the previous work. Selenite was bound to the material via inner-sphere complexation (via oxygen) to the adsorption sites of the amorphous Fe(III) and Mn(III) oxides. This anion was attracted via bidentate binuclear corner-sharing coordination between SeO3(2-) trigonal pyramids and both FeO6 and MnO6 octahedra; however, the adsorption sites of Fe(III) hydrous oxides played a leading role in selenite removal. The contribution of the adsorption sites of Mn(III) oxide increased as the pH decreased from 8 to 6. Because most minerals have a complex structure (they are seldom based on individual substances) of various crystallinity, this work is equally relevant to environmental science and environmental technology because it shows how various solid phases control cycling of chemical elements in the environment.
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Ayyamperumal, T; Jonathan, M P; Srinivasalu, S; Armstrong-Altrin, J S; Ram-Mohan, V
2006-09-01
An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.
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Oxidative removal of Mn(II) from solution catalysed by the γ-FeOOH (lepidocrocite) surface
NASA Astrophysics Data System (ADS)
Sung, Windsor; Morgan, James J.
1981-12-01
A laboratory study was undertaken to ascertain the role of surface catalysis in Mn(II) oxidative removal. γ-FeOOH, a ferric oxyhydroxide formed by O2 oxidation of ferrous iron in solution, was studied in the following ways: surface charge characteristics by acid base titration, adsorption of Mn(II) and surface oxidation of Mn(II). A rate law was formulated to account for the effects of pH and the amount of surface on the surface oxidation rate of Mn(II). The presence of milli-molar levels of γ-FeOOH was shown to reduce significantly the half-life of Mn(II) in 0.7 M NaCl from hundreds of hours to hours. The numerical values of the surface rate constants for the γ-FeOOH and that reported for colloidal MnO2 are comparable in order of magnitude.
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Mössbauer and XRD study of novel quaternary Sn-Fe-Co-Ni electroplated alloy
NASA Astrophysics Data System (ADS)
Kuzmann, E.; Sziráki, L.; Stichleutner, S.; Homonnay, Z.; Lak, G. B.; El-Sharif, M.; Chisholm, C. U.
2017-11-01
Constant current electrochemical deposition technique was used to obtain quaternary alloys of Sn-Fe-Co-Ni from a gluconate electrolyte, which to date have not been reported in the literature. For the characterization of electroplated alloys, 57Fe and 119Sn Conversion Electron Mössbauer Spectroscopy (CEMS), XRD and SEM/EDAX were used. XRD revealed the amorphous character of the novel Sn-Fe-Co-Ni electrodeposited alloys. 57Fe Mössbauer spectrum of quaternary deposit with composition of 37.0 at% Sn, 38.8 at% Fe, 16.8 at% Co and 7.4 at% Ni displayed a magnetically split sextet (B = 28.9T) with broad lines typical of iron bearing ferromagnetic amorphous alloys. Magnetically split 119Sn spectra reflecting a transferred hyperfine field (B = 2.3T) were also observed. New quaternary Sn-Fe-Co-Ni alloys were successfully prepared.
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NASA Astrophysics Data System (ADS)
Abreu, Neyda M.
2016-12-01
A number of different classifications have been proposed for the CR chondrites; this study aims at reconciling these different schemes. Mineralogy-based classification has proved particularly challenging for weakly to moderately altered CRs because incipient mineral replacement and elemental mobilization arising from aqueous alteration only affected the most susceptible primary phases, which are generally located in the matrix. Secondary matrix phases are extremely fine-grained (generally sub-micron) and heterogeneously mixed with primary nebular materials. Compositional and isotopic classification parameters are fraught with confounding factors, such as terrestrial weathering, impact processes, and variable abundance of clasts from different regions of the CR parent body or from altogether different planetary bodies. Here, detailed TEM observations from eighteen FIB sections retrieved from the matrices of nine Antarctic CR chondrites (EET 96259, GRA 95229, GRO 95577, GRO 03116, LAP 02342, LAP 04516, LAP 04720, MIL 07525, and MIL 090001) are presented, representing a range of petrologic types. Amorphous Fe-Mg silicates are found to be the dominant phase in all but the most altered CR chondrite matrices, which still retain significant amounts of these amorphous materials. Amorphous Fe-Mg silicates are mixed with phyllosilicates at the nanometer scale. The ratio of amorphous Fe-Mg silicates to phyllosilicates decreases as: (1) the size of phyllosilicates, (2) abundance of magnetite, and (3) replacement of Fe-Ni sulfides increase. Carbonates are only abundant in the most altered CR chondrite, GRO 95577. Nanophase Fe-Ni metal and tochilinite are present small abundances in most CR matrices. Based on the presence, abundance and size of phyllosilicates with respect to amorphous Fe-Mg silicates, the sub-micron features of CR chondrites have been linked to existing classification sequences, and possible reasons for inconsistencies among classification schemes are discussed.
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Metallic glass coating on metals plate by adjusted explosive welding technique
NASA Astrophysics Data System (ADS)
Liu, W. D.; Liu, K. X.; Chen, Q. Y.; Wang, J. T.; Yan, H. H.; Li, X. J.
2009-09-01
Using an adjusted explosive welding technique, an aluminum plate has been coated by a Fe-based metallic glass foil in this work. Scanning electronic micrographs reveal a defect-free metallurgical bonding between the Fe-based metallic glass foil and the aluminum plate. Experimental evidence indicates that the Fe-based metallic glass foil almost retains its amorphous state and mechanical properties after the explosive welding process. Additionally, the detailed explosive welding process has been simulated by a self-developed hydro-code and the bonding mechanism has been investigated by numerical analysis. The successful welding between the Fe-based metallic glass foil and the aluminum plate provides a new way to obtain amorphous coating on general metal substrates.
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Morphological, structural, and spectral characteristics of amorphous iron sulfates
Sklute, E. C.; Jensen, H. B.; Rogers, A. D.; Reeder, R. J.
2018-01-01
Current or past brine hydrologic activity on Mars may provide suitable conditions for the formation of amorphous ferric sulfates. Once formed, these phases would likely be stable under current Martian conditions, particularly at low- to mid-latitudes. Therefore, we consider amorphous iron sulfates (AIS) as possible components of Martian surface materials. Laboratory AIS were created through multiple synthesis routes and characterized with total X-ray scattering, thermogravimetric analysis, scanning electron microscopy, visible/near-infrared (VNIR), thermal infrared (TIR), and Mössbauer techniques. We synthesized amorphous ferric sulfates (Fe(III)2(SO4)3 · ~ 6–8H2O) from sulfate-saturated fluids via vacuum dehydration or exposure to low relative humidity (<11%). Amorphous ferrous sulfate (Fe(II)SO4 · ~1H2O) was synthesized via vacuum dehydration of melanterite. All AIS lack structural order beyond 11 Å. The short-range (<5 Å) structural characteristics of amorphous ferric sulfates resemble all crystalline reference compounds; structural characteristics for the amorphous ferrous sulfate are similar to but distinct from both rozenite and szomolnokite. VNIR and TIR spectral data for all AIS display broad, muted features consistent with structural disorder and are spectrally distinct from all crystalline sulfates considered for comparison. Mössbauer spectra are also distinct from crystalline phase spectra available for comparison. AIS should be distinguishable from crystalline sulfates based on the position of their Fe-related absorptions in the visible range and their spectral characteristics in the TIR. In the NIR, bands associated with hydration at ~1.4 and 1.9 μm are significantly broadened, which greatly reduces their detectability in soil mixtures. AIS may contribute to the amorphous fraction of soils measured by the Curiosity rover. PMID:29675340
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Osborne, Thomas H; McArthur, John M; Sikdar, Pradip K; Santini, Joanne M
2015-04-07
Natural pollution of groundwater by arsenic adversely affects the health of tens of millions of people worldwide, with the deltaic aquifers of SE Asia being particularly polluted. The pollution is caused primarily by, or as a side reaction of, the microbial reduction of sedimentary Fe(III)-oxyhydroxides, but the organism(s) responsible for As release have not been isolated. Here we report the first isolation of a dissimilatory arsenate reducer from sediments of the Bengal Basin in West Bengal. The bacterium, here designated WB3, respires soluble arsenate and couples its reduction to the oxidation of acetate; WB3 is therefore implicated in the process of arsenic pollution of groundwater, which is largely by arsenite. The bacterium WB3 is also capable of reducing dissolved Fe(III) citrate, solid Fe(III)-oxyhydroxide, and elemental sulfur, using acetate as the electron donor. It is a member of the Desulfuromonas genus and possesses a dissimilatory arsenate reductase that was identified using degenerate polymerase chain reaction primers. The sediment from which WB3 was isolated was brown, Pleistocene sand at a depth of 35.2 m below ground level (mbgl). This level was some 3 cm below the boundary between the brown sands and overlying reduced, gray, Holocene aquifer sands. The color boundary is interpreted to be a reduction front that releases As for resorption downflow, yielding a high load of labile As sorbed to the sediment at a depth of 35.8 mbgl and concentrations of As in groundwater that reach >1000 μg/L.
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NASA Astrophysics Data System (ADS)
Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.
2017-01-01
Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.
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High Purity and Yield of Boron Nitride Nanotubes Using Amorphous Boron and a Nozzle-Type Reactor
Kim, Jaewoo; Seo, Duckbong; Yoo, Jeseung; Jeong, Wanseop; Seo, Young-Soo; Kim, Jaeyong
2014-01-01
Enhancement of the production yield of boron nitride nanotubes (BNNTs) with high purity was achieved using an amorphous boron-based precursor and a nozzle-type reactor. Use of a mixture of amorphous boron and Fe decreases the milling time for the preparation of the precursor for BNNTs synthesis, as well as the Fe impurity contained in the B/Fe interdiffused precursor nanoparticles by using a simple purification process. We also explored a nozzle-type reactor that increased the production yield of BNNTs compared to a conventional flow-through reactor. By using a nozzle-type reactor with amorphous boron-based precursor, the weight of the BNNTs sample after annealing was increased as much as 2.5-times with much less impurities compared to the case for the flow-through reactor with the crystalline boron-based precursor. Under the same experimental conditions, the yield and quantity of BNNTs were estimated as much as ~70% and ~1.15 g/batch for the former, while they are ~54% and 0.78 g/batch for the latter. PMID:28788161
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High Purity and Yield of Boron Nitride Nanotubes Using Amorphous Boron and a Nozzle-Type Reactor.
Kim, Jaewoo; Seo, Duckbong; Yoo, Jeseung; Jeong, Wanseop; Seo, Young-Soo; Kim, Jaeyong
2014-08-11
Enhancement of the production yield of boron nitride nanotubes (BNNTs) with high purity was achieved using an amorphous boron-based precursor and a nozzle-type reactor. Use of a mixture of amorphous boron and Fe decreases the milling time for the preparation of the precursor for BNNTs synthesis, as well as the Fe impurity contained in the B/Fe interdiffused precursor nanoparticles by using a simple purification process. We also explored a nozzle-type reactor that increased the production yield of BNNTs compared to a conventional flow-through reactor. By using a nozzle-type reactor with amorphous boron-based precursor, the weight of the BNNTs sample after annealing was increased as much as 2.5-times with much less impurities compared to the case for the flow-through reactor with the crystalline boron-based precursor. Under the same experimental conditions, the yield and quantity of BNNTs were estimated as much as ~70% and ~1.15 g/batch for the former, while they are ~54% and 0.78 g/batch for the latter.
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NASA Astrophysics Data System (ADS)
Breier, J. A.; Toner, B. M.; Fakra, S. C.; Marcus, M. A.; White, S. N.; Thurnherr, A. M.; German, C. R.
2012-07-01
Deep-sea hydrothermal plume particles are known to sequester seawater trace elements and influence ocean-scale biogeochemical budgets. The relative importance of biotic versus abiotic oxidation-reduction and other particle-forming reaction, however, and the mechanisms of seawater trace element sequestration remain unknown. Suspended particulate material was collected from a non-buoyant hydrothermal plume by in situ filtration at 9°50‧N East Pacific Rise during a 3-day, 24 sample, time-series. Twenty-three samples were digested for total elemental analysis. One representative sample was selected for particle-by-particle geochemical analyses including elemental composition by X-ray fluorescence, speciation of Fe, S, and C by 1s X-ray absorption near edge structure spectroscopy, and X-ray diffraction. Consistent with past studies, positive linear correlations were observed for P, V, As, and Cr with Fe in the bulk chemistry. Arsenic was associated with both Fe oxyhydroxides and sulfides but not uniformly distributed among either mineral type. Particle aggregation was common. Aggregates were composed of minerals embedded in an organic matrix; the minerals ranged from <20 nm to >10 μm in diameter. The speciation of major mineral forming elements (Fe, Mn, S) was complex. Over 20 different minerals were observed, nine of which were either unpredicted by thermodynamic modeling or had no close match in the thermodynamic database. Sulfur-bearing phases consisted of polysulfides (S6, S8), and metal sulfides (Fe, Cu, Zn, Mn). Four dominant species, Fe oxyhydroxide, Fe monosulfide, pyrrhotite, and pyrite, accounted for >80% of the Fe present. Particulate Mn was prevalent in both oxidized and reduced minerals. The organic matrix was: (1) always associated with minerals, (2) composed of biomolecules, and (3) rich in S. Possible sources of this S-rich organic matter include entrained near vent biomass and in situ production by S-oxidizing microorganisms. These results indicate that particle aggregation with organic material is prevalent in dispersing hydrothermal plume fluxes, as well as in sinking particulate matter at this site. Particle aggregation and organic coatings can influence the reactivity, transport, and residence time of hydrothermal particles in the water column. Thus a biogeochemical approach is critical to understanding the net effect of hydrothermal fluxes on ocean and sedimentary trace element budgets.
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Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.
1993-01-01
Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.
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NASA Astrophysics Data System (ADS)
Fronczyk, Adam
2007-04-01
In this study, we report on a crystallization behavior of the Fe 95Si 5 metallic glasses using a differential scanning cabrimetry (DSC), and X-ray diffraction. The paper presents the results of experimental investigation of Fe 95Si 5 amorphous alloy, subjected to the crystallizing process by the isothermal annealing. The objective of the experiment was to determine changes in the structural parameters during crystallization process of the examined alloy. Crystalline diameter and the lattice constant of the crystallizing phase were used as parameters to evaluate structural changes in material.
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Durham, Jessica L; Brady, Alexander B; Cama, Christina A; Bock, David C; Pelliccione, Christopher J; Zhang, Qing; Ge, Mingyuan; Li, Yue Ru; Zhang, Yiman; Yan, Hanfei; Huang, Xiaojing; Chu, Yong; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C
2017-08-23
The structure of pristine AgFeO 2 and phase makeup of Ag 0.2 FeO 1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2 O 3 phases) was investigated using synchrotron X-ray diffraction. A new stacking-fault model was proposed for AgFeO 2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2 FeO 1.6 were investigated using ex situ, in situ, and operando characterization techniques. An amorphous γ-Fe 2 O 3 component in the Ag 0.2 FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2 FeO 1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex situ X-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in situ high energy X-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag 0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+y Fe III Fe II y O 2 phase. The Li 1+y Fe III Fe II y O 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2 FeO 1.6 composite, a substantial amorphous γ-Fe 2 O 3 component is observed which discharges to rock salt LiFe 2 O 3 and Fe 0 metal phase in the 3.5-1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.
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Enhanced magnetoimpedance and field sensitivity in microstructure controlled FeSiCuNbB ribbons
NASA Astrophysics Data System (ADS)
Sahoo, Trilochan; Chandra Mishra, Amaresh; Srinivas, V.; Nath, T. K.; Srinivas, M.; Majumdar, B.
2011-10-01
Fe73.5Si13.5Cu1Nb3B9 and Fe77.2Si11.2Cu0.8Nb3.3B7.5 nanocomposite materials consisting of nanocrystalline phase in an amorphous matrix were obtained by heat-treatment of their precursor amorphous ribbons. The influence of structural modifications induced during the heat-treatment on soft magnetic properties and magnetoimpedance (MI) effect have been studied. The structural investigations on both these ribbons revealed the presence of two phases, fine grained Fe3Si phase and a residual amorphous phase on heat-treatment. The maximum MI ratio obtained in the present study is 95% at f = 4 MHz, for the optimized heat-treated Fe77.2Si11.2Cu0.8Nb3.3B7.5 ribbon. This is ascribed to the increase in magnetic permeability and decrease in coercive force and intrinsic resistivity. Moreover, a maximum magnetic field sensitivity (ξ) of 8.3%/Oe at f = 2.5 MHz is obtained, for the optimized nanocrystalline Fe73.5Si13.5Cu1Nb3B9 ribbon. This suggests that tailoring of the nanocrystalline microstructures induced by optimum heat-treatment conditions can result in obtaining excellent combinations of the magnetic permeability and resistivity. Our results indicate that these Fe-based nanocrystalline materials can be ideally used for low magnetic field and high frequency sensor applications.
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Substrate temperature effect on the structural anisotropy in amorphous Tb-Fe films
NASA Astrophysics Data System (ADS)
Harris, V. G.; Hellman, F.; Elam, W. T.; Koon, N. C.
1993-05-01
Using extended x-ray absorption fine structures (EXAFS) measurements we have investigated the atomic environment around the Fe atom in a series of amorphous Tb0.26Fe0.74 films having different magnetic anisotropy energies owing to different deposition temperatures. The polarization properties of synchrotron radiation allowed the separate study of structure parallel and perpendicular to the sample plane. An anisotropy between these two structures was observed. Modeling results indicate this anisotropy is due to anisotropic pair correlations where the Fe-Fe pairs are statistically preferred in-plane and the Fe-Tb pairs out-of-plane. The amplitude of this anisotropy scales with both the substrate temperature and the magnetic anisotropy energy. A ≊1% in-plane compression of the Fe-Fe distance was measured between the in-plane and out-of-plane structure of the sample grown at 77 K. This sample had no detectable local chemical anisotropy suggesting that intrinsic stress plays an important role in determining its magnetic anisotropy.
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Magnetic and transport properties of Fe-based nanocrystalline materials
NASA Astrophysics Data System (ADS)
Barandiarán, J. M.
1994-01-01
Fe-rich amorphous alloys containing late transition metals like Nb, V, Zr,..., sometimes with the addition of Cu, can crystallize in ultrafine grains of a crystalline phase, a few nanometers in diameter, embedded in a disordered matrix. In such state they have shown excellent soft magnetic properties for technical applications, rising the interest for deep studies. In this paper, recent work on some Fe-Nb and Fe-Zr based alloys both in amorphous state and after several degrees of nanocrystallization is presented. The nanocrystallization process has been achieved by conventional heat treatments (about 1 h at temperatures around 400-500 °C in a controlled atmosphere furnance) as well as by Joule heating using an electrical current flowing through the sample. Magnetic measurements, electrical resistivity, x-rays diffraction and 57Fe Mössbauer spectroscopy were used in the study of the crystalline phases appearing after the thermal treatments. The basic magnetic and transport properties of the nanocrystals do not differ appreciably from their bulk values. The magnetic anisotropy, however, is very sensitive to grain size and to the intergranular magnetic coupling. The effect of such coupling is deduced from the coercivity changes at the Curie Temperature of the amorphous matrix remaining after nanocrystallization.
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High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.
Wang, Yuesheng; Yang, Shi-Ze; You, Ya; Feng, Zimin; Zhu, Wen; Gariépy, Vincent; Xia, Jiexiang; Commarieu, Basile; Darwiche, Ali; Guerfi, Abdelbast; Zaghib, Karim
2018-02-28
Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO 4 and amorphous FePO 4 ·2H 2 O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO 4 ·2H 2 O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO 4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO 4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO 4 ·2H 2 O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO 4 anodes commercially viable configurations for aqueous lithium-ion batteries.
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Analysis of the Glass-Forming Ability of Fe-Er Alloys, Based on Thermodynamic Modeling
NASA Astrophysics Data System (ADS)
Arutyunyan, N. A.; Zaitsev, A. I.; Dunaev, S. F.; Kalmykov, K. B.; El'nyakov, D. D.; Shaposhnikov, N. G.
2018-05-01
The Fe-Er phase diagram and thermodynamic properties of all its phases are assessed by means of self-consistent analysis. To refine the data on phase equilibria in the Fe-Er system, an investigation is performed in the 10-40 at % range of Er concentrations. The temperature-concentration dependences of the thermodynamic properties of a melt are presented using the model of ideal associated solutions. Thermodynamic parameters of each phase are obtained, and the calculated results are in agreement with available experimental data. The correlation between the thermodynamic properties of liquid Fe-Er alloys and their tendency toward amorphization are studied. It is shown that compositions of amorphous alloys prepared by melt quenching coincide with the ranges of concentration with the predominance of Fe3Er and FeEr2 associative groups that have large negative entropies of formation.
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NASA Astrophysics Data System (ADS)
Menushenkov, V. P.; Shchetinin, I. V.; Chernykh, S. V.; Savchenko, A. G.; Gorshenkov, M. V.; Zhukov, D. G.
2017-10-01
The effect of severe plastic deformation (SPD) by torsion and subsequent annealing on the structure and magnetic properties of the cast Nd9.5Fe84.5B6 alloy is studied. SPD by torsion is shown to lead to partial amorphization of the Nd2Fe14B phase and the precipitation of α-Fe; subsequent annealing results in the crystallization of the amorphous phase and the formation of a nanocomposite Nd2Fe14B/α-Fe structure. After SPD by torsion at 20 revolutions and annealing at 873 K, the (101) texture is formed; in this case, the coercive force is H c = 360 kA/m and the maximum energy product is ( BH) max = 166 kJ/m3. The residual magnetization and the squareness ratio of the hysteretic loop of the textured alloy decrease as the ambient temperature decreases.
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NASA Astrophysics Data System (ADS)
Zhou, Z.; Wang, L.; He, D. Y.; Wang, F. C.; Liu, Y. B.
2011-01-01
A Fe48Cr15Mo14C15B6Y2 alloy with high glass forming ability (GFA) was selected to prepare amorphous metallic coatings by atmospheric plasma spraying (APS). The as-deposited coatings present a dense layered structure and low porosity. Microstructural studies show that some nanocrystals and a fraction of yttrium oxides formed during spraying, which induced the amorphous fraction of the coatings decreasing to 69% compared with amorphous alloy ribbons of the same component. High thermal stability enables the amorphous coatings to work below 910 K without crystallization. The results of electrochemical measurement show that the coatings exhibit extremely wide passive region and relatively low passive current density in 3.5% NaCl and 1 mol/L HCl solutions, which illustrate their superior ability to resist localized corrosion. Moreover, the corrosion behavior of the amorphous coatings in 1 mol/L H2SO4 solution is similar to their performance under conditions containing chloride ions, which manifests their flexible and extensive ability to withstand aggressive environments.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Aiyong; Lin, Bo; Zhang, Hanlei
2017-01-01
Three series of Cr-based mixed oxides (Cr-Co, Cr-Fe, and Cr-Ni oxides) with high specific surface areas and amorphous textures were synthesized using a novel sol-gel method. These mixed oxides, in comparison to their pure metal oxide (CrOx, Co3O4, FeOx and NiO) counterparts, display enhanced performance for catalytic oxidation of low-concentration NO at room temperature. The best performing catalysts achieve 100% NO conversion for ~30 h of operation at a high space velocity of 45,000 ml g-1 h-1. The amorphous structure was found to be critical for these catalysts to maintain high activity and durability. Control of Cr/M (M=Co, Fe andmore » Ni) molar ratio, nitrate precursor decomposition temperature and catalyst calcination temperature was key to the synthesis of these highly active catalysts.« less
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Durham, Jessica L.; Brady, Alexander B.; Cama, Christina A.; ...
2017-08-02
Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2O 3 component in the Ag 0.2FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2FeO 1.6 composites demonstrated differences in the structuralmore » evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+yFe IIIFe IIyO 2 phase. The Li 1+yFe IIIFe IIyO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2FeO 1.6 composite, a substantial amorphous γ-Fe 2O 3 component is observed which discharges to rock salt LiFe 2O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Durham, Jessica L.; Brady, Alexander B.; Cama, Christina A.
Here, the structure of pristine AgFeO 2 and phase makeup of Ag 0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO 2 and amorphous γ-Fe 2O 3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO 2 and Ag 0.2FeO 1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe 2O 3 component in the Ag 0.2FeO 1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO 2 and Ag 0.2FeO 1.6 composites demonstrated differences in the structuralmore » evolution of the nanocrystalline AgFeO 2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag + to Ag0 and partial reduction of Fe 3+ to Fe 2+ occur on reduction to 1.0 V, resulting in a Li 1+yFe IIIFe IIyO 2 phase. The Li 1+yFe IIIFe IIyO 2 phase can then reversibly cycle between Fe 3+ and Fe 2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag 0.2FeO 1.6 composite, a substantial amorphous γ-Fe 2O 3 component is observed which discharges to rock salt LiFe 2O 3 and Fe 0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO 2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less
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Nanocrystal dispersed amorphous alloys
NASA Technical Reports Server (NTRS)
Perepezko, John H. (Inventor); Allen, Donald R. (Inventor); Foley, James C. (Inventor)
2001-01-01
Compositions and methods for obtaining nanocrystal dispersed amorphous alloys are described. A composition includes an amorphous matrix forming element (e.g., Al or Fe); at least one transition metal element; and at least one crystallizing agent that is insoluble in the resulting amorphous matrix. During devitrification, the crystallizing agent causes the formation of a high density nanocrystal dispersion. The compositions and methods provide advantages in that materials with superior properties are provided.
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Ji, Xuqiang; Hao, Shuai; Qu, Fengli; Liu, Jingquan; Du, Gu; Asiri, Abdullah M; Chen, Liang; Sun, Xuping
2017-06-14
The exploration of high-performance and earth-abundant water oxidation catalysts operating under mild conditions is highly attractive and challenging. In this communication, core-shell CoFe 2 O 4 @Co-Fe-Bi nanoarray on carbon cloth (CoFe 2 O 4 @Co-Fe-Bi/CC) was successfully fabricated by in situ surface amorphization of CoFe 2 O 4 nanoarray on CC (CoFe 2 O 4 /CC). As a 3D water oxidation electrode, CoFe 2 O 4 @Co-Fe-Bi/CC shows outstanding activity with an overpotential of 460 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 0.1 M potassium borate (pH 9.2). Notably, it also demonstrates superior long-term durability for at least 20 h with 96% Faradic efficiency. Density functional theory calculations indicate that the conversion from OOH* to O 2 is the rate-limiting step and the high water oxidation activity of CoFe 2 O 4 @Co-Fe-Bi/CC is associated with the lower free energy of 1.84 eV on a Co-Fe-Bi shell.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
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Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...
2015-09-05
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
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Hiller, Edgar; Petrák, Marián; Tóth, Roman; Lalinská-Voleková, Bronislava; Jurkovič, L'ubomír; Kučerová, Gabriela; Radková, Anežka; Sottník, Peter; Vozár, Jaroslav
2013-11-01
Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Markušovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation-equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite > pyrite > tetrahedrite>arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16-8.12) and the waters (pH 7.00-8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu>Sb>Hg>As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52-7.96) and low concentrations of dissolved metal(loid)s (<5-7.0 μg/L Cu, <0.1-0.3 μg/L Hg, 5.0-16 μg/L As, and 5.0-43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.
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Green rusts synthesis by coprecipitation of Fe II-Fe III ions and mass-balance diagram
NASA Astrophysics Data System (ADS)
Ruby, Christian; Aïssa, Rabha; Géhin, Antoine; Cortot, Jérôme; Abdelmoula, Mustapha; Génin, Jean-Marie
2006-06-01
A basic solution is progressively added to various mixed Fe II-Fe III solutions. The nature and the relative quantities of the compounds that form can be visualised in a mass-balance diagram. The formation of hydroxysulphate green rust {GR( SO42-)} is preceded by the precipitation of a sulphated ferric basic salt that transforms in a badly ordered ferric oxyhydroxide. Then octahedrally coordinated Fe II species and SO42- anions are adsorbed on the FeOOH surface and GR( SO42-) is formed at the solid/solution interface. By using the same method of preparation, other types of green rust were synthesised, e.g. hydroxycarbonate green rust {GR( CO32-)}. Like other layered double hydroxides, green rusts obey the general chemical formula [ṡ[ṡmHO]x+ with x⩽1/3. Al-substituted hydroxysulphate green rust consists of small hexagonal crystals with a lateral size ˜50 nm, which is significantly smaller than the size of the GR( SO42-) crystals (˜500 nm). To cite this article: C. Ruby et al., C. R. Geoscience 338 (2006).
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Structure and magnetic properties of Nd2Fe14B fine particles produced by spark erosion
NASA Astrophysics Data System (ADS)
Wan, H.; Berkowitz, A. E.
1994-11-01
At present Nd2Fe14B is the best permanent magnet because of its extremely high coercivity and energy product. Optimum properties of Nd2Fe14B magnets can be attained by producing single domain particles, and then aligning and compacting them. Due to the reactivity of the Nd constitutent, it is challenging to produce and handle a large amount of fine particles of this material. We have prepared fine particles of Nd2Fe14B by spark erosion with various dielectric media. Yield, size, size distribution, structure, and magnetic properties are discussed. The Nd2Fe14B particles were made by the sharker pot spark erosion method. Relaxation oscillators or a pulse generator were used to power the park erosion. Commercial Neomax 35 was employed as the primary material. The dielectric media were liquid Ar, Ar gas, and hydrocarbons, which provided an oxygen free environment. Structure and size were studied by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and x-ray diffraction. Magnetic properties were measured by vibrating sample magnetometer (VSM) with temperatures in range of 4.2-1200 K. The particles produced in these three different dielectric media had different microstructures and crystal structures. The particles made in Ar gas were pure Nd2Fe14B phase. The particles made in liquid Ar were a mixture of amorphous and crystalline Nd2Fe14B, because the liquid Ar provided a much higher quench rate than Ar gas, which produced some amorphous Nd2Fe14B. Upon annealing, the amorphous particles became crystalline. The fine particles produced in hydrocarbons, such as pentane and dodecane, had more complex mixed phases, since the rare earth reacted with the hydrocarbons during the sparking process. The phases were NdC2, alpha-Fe, and amorphous and crystalline Nd2Fe14B. The effects of power parameters, such as voltage and capacitance, on particle size were investigated. Particle sizes from 20 nm to 50 microns were obtained.
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The composition of secondary amorphous phases under different environmental conditions
NASA Astrophysics Data System (ADS)
Smith, R.; Rampe, E. B.; Horgan, B. H. N.; Dehouck, E.; Morris, R. V.
2017-12-01
X-ray diffraction (XRD) patterns measured by the CheMin instrument on the Mars Science Laboratory Curiosity rover demonstrate that amorphous phases are major components ( 15-60 wt%) of all rock and soil samples in Gale Crater. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., silica, ferrihydrite) phases. Secondary amorphous phases are frequently found as weathering products in soils on Earth, but these materials remain poorly characterized. Here we study a diverse suite of terrestrial samples including: sediments from recently de-glaciated volcanoes (Oregon), modern volcanic soils (Hawaii), and volcanic paleosols (Oregon) in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of amorphous phases. We combine bulk XRD mineralogy with bulk chemical compositions (XRF) to calculate the abundance and bulk composition of the amorphous materials in our samples. We then utilize scanning transmission electron microscopy (STEM) and energy dispersive x-ray spectroscopy (EDS) to study the composition of individual amorphous phases at the micrometer scale. XRD analyses of 8 samples thus far indicate that the abundance of amorphous phases are: modern soils (20-80 %) > paleosols (15-40 %) > glacial samples (15-30 %). Initial calculations suggest that the amorphous components consist primarily of SiO2, Al2O3, TiO2, FeO and Fe2O3, with minor amounts of other oxides (e.g., MgO, CaO, Na2O). Compared to their respective crystalline counterparts, calculations indicate bulk amorphous components enriched in SiO2 for the glacial sample, and depleted in SiO2 for the modern soil and paleosol samples. STEM analyses reveal that the amorphous components consist of a number of different phases. Of the two samples analyzed using STEM thus far, the secondary amorphous phases have compositions with varying ratios of SiO2, Al2O3, TiO2, and Fe-oxides, consistent with mass balance calculation results, but inconsistent with well-known amorphous phase compositions (e.g., allophane, ferrihydrite). These results show that a number of secondary amorphous phases can form within a single soil environment. Continued analysis can help determine whether compositional trends can be linked to environmental factors.
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Size and shape dependence of CO adsorption sites on sapphire supported Fe microcrystals
NASA Technical Reports Server (NTRS)
Papageorgopoulos, C.; Heinemann, K.
1985-01-01
The surface structure and stoichiometry of alumina substrates, as well as the size, growth characteristics, and shape of Fe deposits on sapphire substrates have been investigated by low energy electron diffraction (LEED), Auger electron spectroscopy, electron energy loss spectroscopy, and X-ray photoemission spectroscopy (XPS), as well as work function measurements, in conjunction with transition electron microscopy observations. The substrates used in this work were the following: (1) new, clean Al2O3; (2) same surface amorphized by Ar ion bombardment; (3) same surface regenerated by 650 C annealing; (4) amorphous alumina films on Ta slab; and (5) polycrystal alumina films, obtained by heating amorphous films to 600 C. Substrate cleaning was found to be most effective in producing a reproducible surface upon oxygen RF plasma treatment. The Fe nucleation and growth process was found to depend strongly on the type of substrate surface and deposition conditions. Ar ion bombardment under beam flooding, and subsequent annealing at 650 C was found an effective means to restore the original Al2O3 (1102) surface for renewed Fe deposition.
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Resistivity changes of some amorphous alloys undergoing nanocrystallization
NASA Astrophysics Data System (ADS)
Barandiarán, J. M.; Fernández Barquín, L.; Sal, J. C. Gómez; Gorría, P.; Hernando, A.
1993-10-01
The electrical resistivity of amorphous alloys with compositions: Fe 73.5Nb 3Cu 1Si 13.5B 9, Fe 86Zr 7Cu 1B 6 and Co 80Nb 8B 12 has been studied in the temperature range from 300 to 1100 K, where crystallization occurs. The products of crystallization and the grain size have been studied by X-ray diffraction. In a first step, all the alloys crystallize with small grains of a few nanometers in diameter (nanocrystalline state), and the resistivity behavior at this process accounts for the difference between the amorphous and nanocrystalline phases. The nanocrystalline phases are: α-Fe-Si, α-Fe and fcc Co for the three compounds studied respectively. A second process, at which grain growth and precipitation of intermetallic compounds and borides takes place, has been found for all the alloys. The resistivity is sensitive, not only to the total transformed sample amount, but to the topological distribution of the crystalline phases, and therefore shows a more complex behavior than other well established techniques, as differential scanning calorimetry. This supplementary information given by the resistivity is also discussed.
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NASA Astrophysics Data System (ADS)
Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel
2002-05-01
Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.
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NASA Astrophysics Data System (ADS)
Verma, Swati; Mukherjee, Abhijit; Mahanta, Chandan; Choudhury, Runti; Mitra, Kaushik
2016-09-01
The present study interprets the groundwater solute chemistry, hydrogeochemical evolution, arsenic (As) enrichment and aquifer characterization in Brahmaputra River Basin (BRB) involving three geologically and tectono-morphically distinct regions located in northeastern India. These study regions consist of the northwestern (NW) and the northern (N) region, both located along the western and eastern parts of Eastern Himalayas and the southern (S) region (near Indo-Burmese Range and Naga hills) of the Brahmaputra basin which show distinct tectonic settings and sediment provenances in the Himalayan orogenic belt. Stable isotopic composition (δ2H and δ18O) in groundwater suggests that some evaporation may have taken place through recharging of ground water in the study areas. The major-ion composition shows that groundwater composition of the NW and N parts are between Casbnd HCO3 and Casbnd Nasbnd HCO3 while the S-region is dominated by Nasbnd Casbnd HCO3 hydrochemical facies. The major mineralogical composition of aquifer sediments indicates the dominant presence of iron(Fe)-oxide and oxyhydroxides, mica (muscovite and biotite), feldspar, pyroxene, amphibole, abundance of quartz and clay minerals whereas clay is predominantly present in sediments of S-aquifers. These mafic minerals, aluminosilicates and clay minerals might offer available reactive surface for As-adsorption and co-precipitatation with amorphous Fe. These associated adsorbed and co-precipitated As might be released due to reductive dissolution of Fe-oxide and oxyhydroxides in groundwater. These minerals are assumed to be possible sources of As in groundwater. The stability diagrams of groundwater data suggest that solute might have been introduced into groundwater from weathering of K-feldspar, plagioclase, pyroxene of Himalayan rocks, the Siwalik Group and Eastern Syntaxes in NW and N-regions. However, basic cations might be derived from weathering of K-feldspar, plagioclase, pyroxene and olivine those being major constituents in a gabbroic complex (ophiolite) and basalt terrain in S-region. The aquifers of S-region are severely contaminated with dissolved As compared to NW and N regions. Almost more than 92% of groundwater samples in the southern part (maximum 5.53 μM or 415 μg/L) are enriched with As, which draws a distinct difference from the NW and N parts of BRB aquifers. The redox-sensitive solutes (i.e., Fe, Mn, HCO3- and TOC) are positively correlated with As in NW and N-parts; whereas EH shows negative to very weak positive correlation which suggests that a redox-dependent mobilization plays important role in As liberation in NW and N parts of the basin. However, As in southern aquifers is not showing any correlation or weak negative correlation with redox-sensitive solutes; suggesting that multiple reactions and hydrogeochemical processes and their interaction control As mobilization and fate in the S-region of BRB. The occurrence of high concentrations of arsenic in groundwater of Brahmaputra basin is described through a crustal recycling model and tectonic movement between the Indian-Eurasian plates and Burmese micro-continents. As-enriched groundwater in Himalayan foreland basin in the BRB is probably a result of crustal evolution through which As is subsequently mobilized from aquifer matrix to solution in groundwater by water-sediment reaction under favorable biogeochemical conditions. The results of the study indicate geological control (i.e. change in lithofacies, tectonic set-up) on groundwater chemistry and distribution of redox-sensitive solutes such as As.
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Fe-based bulk amorphous alloys with iron contents as high as 82 at%
NASA Astrophysics Data System (ADS)
Li, Jin-Feng; Liu, Xue; Zhao, Shao-Fan; Ding, Hong-Yu; Yao, Ke-Fu
2015-07-01
Fe-based bulk amorphous alloys (BAAs) with high Fe contents are advantageous due to their high saturation magnetization and low cost. However, preparing Fe-based BAAs with Fe contents higher than 80 at% is difficult due to their poor glass forming abilities (GFA). In this study, an Fe81P8.5C5.5B2Si3 BAA with a diameter of 1 mm and a saturation magnetization of 1.56 T was successfully prepared using the fluxing and copper mold casting methods. In addition, by introducing a small amount of elemental Mo to the alloy, an Fe82Mo1P6.5C5.5B2Si3 BAA rod with a diameter of 1 mm, a high saturation magnetization of 1.59 T, a high yield stress of 3265 MPa, and a clear plasticity of 1.3% was prepared in the same way. The cost effectiveness and good magnetic properties of these newly-developed Fe-based BAAs with Fe contents as high as 82 at% would be advantageous and promising for industrial applications.
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Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.
Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine
2016-04-05
The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.
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Aronhime, Natan; DeGeorge, Vincent; Keylin, Vladimir; ...
2017-07-25
Here, Fe-Ni-based metal amorphous nanocomposites with a range of compositions (Fe 100–xNi x) 80Nb 4Si 2B 14 (30 ≤ x ≤ 70) are investigated for motor and transformer applications, where it is beneficial to have tunable permeability. It is shown that strain annealing offers an effective method for tuning permeability in these alloys. For an Fe-rich alloy, permeability increased from 4000 to 16,000 with a positive magnetostriction. In a Ni-rich alloy, permeability decreased from 290 to 40 with a negative magnetostriction. Significant elongations (above 60%) are observed during strain annealing at high stress. Crystallization products have been determined in allmore » alloys heated to 480°C. γ-FeNi is formed in all alloys, while (Fe 30Ni 70) 80Nb 4Si 2B 14 also undergoes secondary crystallization at temperatures of approximately 480°C to form a phase with the Cr 23C 6-type structure and a likely composition of Fe 21Nb 2B 6. Toroidal losses have been measured for (Fe 70Ni 30) 80Nb 4Si y B 16–y (0 ≤ y ≤ 3) at various annealing temperatures. At an induction of 1 T and frequency of 400 Hz and 1 kHz, the toroidal losses obtained are W 1.0T, 400 Hz = 0.9 W/kg and W 1.0T, 1 kHz = 2.3 W/kg, respectively. These losses are lower than losses recently reported for state of the art 3.0% and 6.5% silicon steels, a Metglas Fe-based amorphous alloy, and some Fe-based nanocomposites.« less
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NASA Astrophysics Data System (ADS)
Aronhime, Natan; DeGeorge, Vincent; Keylin, Vladimir; Ohodnicki, Paul; McHenry, Michael E.
2017-11-01
Fe-Ni-based metal amorphous nanocomposites with a range of compositions (Fe100- x Ni x )80Nb4Si2B14 (30 ≤ x ≤ 70) are investigated for motor and transformer applications, where it is beneficial to have tunable permeability. It is shown that strain annealing offers an effective method for tuning permeability in these alloys. For an Fe-rich alloy, permeability increased from 4000 to 16,000 with a positive magnetostriction. In a Ni-rich alloy, permeability decreased from 290 to 40 with a negative magnetostriction. Significant elongations (above 60%) are observed during strain annealing at high stress. Crystallization products have been determined in all alloys heated to 480°C. γ-FeNi is formed in all alloys, while (Fe30Ni70)80Nb4Si2B14 also undergoes secondary crystallization at temperatures of approximately 480°C to form a phase with the Cr23C6-type structure and a likely composition of Fe21Nb2B6. Toroidal losses have been measured for (Fe70Ni30)80Nb4Si y B16- y (0 ≤ y ≤ 3) at various annealing temperatures. At an induction of 1 T and frequency of 400 Hz and 1 kHz, the toroidal losses obtained are W1.0T, 400 Hz = 0.9 W/kg and W1.0T, 1 kHz = 2.3 W/kg, respectively. These losses are lower than losses recently reported for state of the art 3.0% and 6.5% silicon steels, a Metglas Fe-based amorphous alloy, and some Fe-based nanocomposites.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Aronhime, Natan; DeGeorge, Vincent; Keylin, Vladimir
Here, Fe-Ni-based metal amorphous nanocomposites with a range of compositions (Fe 100–xNi x) 80Nb 4Si 2B 14 (30 ≤ x ≤ 70) are investigated for motor and transformer applications, where it is beneficial to have tunable permeability. It is shown that strain annealing offers an effective method for tuning permeability in these alloys. For an Fe-rich alloy, permeability increased from 4000 to 16,000 with a positive magnetostriction. In a Ni-rich alloy, permeability decreased from 290 to 40 with a negative magnetostriction. Significant elongations (above 60%) are observed during strain annealing at high stress. Crystallization products have been determined in allmore » alloys heated to 480°C. γ-FeNi is formed in all alloys, while (Fe 30Ni 70) 80Nb 4Si 2B 14 also undergoes secondary crystallization at temperatures of approximately 480°C to form a phase with the Cr 23C 6-type structure and a likely composition of Fe 21Nb 2B 6. Toroidal losses have been measured for (Fe 70Ni 30) 80Nb 4Si y B 16–y (0 ≤ y ≤ 3) at various annealing temperatures. At an induction of 1 T and frequency of 400 Hz and 1 kHz, the toroidal losses obtained are W 1.0T, 400 Hz = 0.9 W/kg and W 1.0T, 1 kHz = 2.3 W/kg, respectively. These losses are lower than losses recently reported for state of the art 3.0% and 6.5% silicon steels, a Metglas Fe-based amorphous alloy, and some Fe-based nanocomposites.« less
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Synthesizing skyrmion bound pairs in Fe-Gd thin films
Lee, J. C. T.; Chess, J. J.; Montoya, S. A.; ...
2016-07-11
Here, we show that properly engineered amorphous Fe-Gd alloy thin films with perpendicular magnetic anisotropy exhibit bound pairs of like-polarity, opposite helicity skyrmions at room temperature. Magnetic mirror symmetry planes present in the stripe phase, instead of chiral exchange, determine the internal skyrmion structure and the net achirality of the skyrmion phase. Our study shows that stripe domain engineering in amorphous alloy thin films may enable the creation of skyrmion phases with technologically desirable properties.
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Synthesis and characterization of bulk metallic glasses prepared by laser direct deposition
NASA Astrophysics Data System (ADS)
Ye, Xiaoyang
Fe-based and Zr-based metallic glasses have attracted extensive interest for structural applications due to their excellent glass forming ability, superior mechanical properties, unique thermal and corrosion properties. In this study, the feasibility of synthesizing metallic glasses with good ductility by laser direct deposition is explored. Both in-situ synthesis with elemental powder mixture and ex-situ synthesis with prealloyed powder are discussed. Microstructure and properties of laser direct deposited metallic glass composites are analyzed. Synthesis of Fe-Cr-Mo-W-Mn-C-Si-B metallic glass composite with a large fraction of amorphous phase was accomplished using laser direct deposition. X-ray diffraction (XRD) and transmission electron microscopy investigations revealed the existence of amorphous structure. Microstructure analyses by optical microscopy and scanning electron microscopy (SEM) indicated the periodically repeated microstructures of amorphous and crystalline phases. Partially crystallized structure brought by laser reheating and remelting during subsequent laser scans aggregated in the overlapping area between each scan. XRD analysis showed that the crystalline particle embedded in the amorphous matrix was Cr 1.07Fe18.93 phase. No significant microstructural differences were found from the first to the last layer. Microhardness of the amorphous phase (HV0.2 1591) showed a much higher value than that of the crystalline phase (HV0.2 947). Macrohardness of the top layer had a value close to the microhardness of the amorphous region. Wear resistance property of deposited layers showed a significant improvement with the increased fraction of amorphous phase. Zr65Al10Ni10Cu15 amorphous composites with a large fraction of amorphous phase were in-situ synthesized by laser direct deposition. X-ray diffraction confirmed the existence of both amorphous and crystalline phases. Laser parameters were optimized in order to increase the fraction of amorphous phase. The microstructure analysis by scanning electron microscopy revealed the deposited structure was composed of periodically repeated amorphous and crystalline phases. Overlapping regions with nanoparticles aggregated were crystallized by laser reheating and remelting processes during subsequent laser scans. Vickers microhardness of the amorphous region showed around 35% higher than that of crystalline region. Average hardness obtained by a Rockwell macrohardness tester was very close to the microhardness of the amorphous region. The compression test showed that the fracture strain of Zr65Al10Ni10Cu15 amorphous composites was enhanced from less than 2% to as high as 5.7%, compared with fully amorphous metallic glass. Differential scanning calorimetry test results further revealed the amorphous structure and glass transition temperature Tg was observed to be around 655K. In 3 mol/L NaCl solution, laser direct deposited amorphous composites exhibited distinctly improved corrosion resistance, compared with fully-crystallized samples.
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Simon, N.S.; Bricker, O.P.; Newell, W.; McCoy, J.; Morawe, R.
2005-01-01
This paper compares phosphorus (P) concentrations in sediments from two watersheds, one with, and one without, intensive animal agriculture. The watersheds are in the coastal plain of the Chesapeake Bay and have similar physiographic characteristics. Agriculture in the Pocomoke River, MD, watershed supplied 2.7 percent of all broiler chickens produced in the USA in 1997. Poultry litter is an abundant, local source of manure for crops. Broiler chickens are not produced in the Popes Creek, VA, watershed and poultry manure is, therefore, not a major source of fertilizer. The largest concentrations of P in sediment samples are found in floodplain and main-stem bottom sediment in both watersheds. Concentrations of total P and P extracted with 1N HCl are significantly larger in main-stem bottom sediments from the Pocomoke River than in main-stem bottom sediments from Popes Creek. Larger concentrations of P are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Pocomoke River watershed than are associated with what are potentially redox sensitive iron oxyhydroxides in sediment samples from the Popes Creek watershed. Data for P and iron (Fe) concentrations in sediments from the Popes Creek watershed provide a numerical framework (baseline) with which to compare P and Fe concentrations in sediment from the Pocomoke River watershed. ?? Springer 2005.
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Dissimilatory reduction and transformation of ferrihydrite-humic acid coprecipitates.
Shimizu, Masayuki; Zhou, Jihai; Schröder, Christian; Obst, Martin; Kappler, Andreas; Borch, Thomas
2013-01-01
Organic matter (OM) is present in most terrestrial environments and is often found coprecipitated with ferrihydrite (Fh). Sorption or coprecipitation of OM with Fe oxides has been proposed to be an important mechanism for long-term C preservation. However, little is known about the impact of coprecipitated OM on reductive dissolution and transformation of Fe(III) (oxyhydr)oxides. Thus, we study the effect of humic acid (HA) coprecipitation on Fh reduction and secondary mineral formation by the dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens strain CN32. Despite similar crystal structure for all coprecipitates investigated, resembling 2-line Fh, the presence of coprecipitated HA resulted in lower specific surface areas. In terms of reactivity, coprecipitated HA resulted in slower Fh bioreduction rates at low C/Fe ratios (i.e., C/Fe ≤ 0.8), while high C/Fe ratios (i.e., C/Fe ≥ 1.8) enhanced the extent of bioreduction compared to pure Fh. The coprecipitated HA also altered the secondary Fe mineralization pathway by inhibiting goethite formation, reducing the amount of magnetite formation, and increasing the formation of a green rust-like phase. This study indicates that coprecipitated OM may influence the rates, pathway, and mineralogy of biogeochemical Fe cycling and anaerobic Fe respiration within soils.
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Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination Processes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Satish C. B. Myneni
2005-12-13
Siderophores are biological macromolecules (400-2000 Da) released by bacteria in iron limiting situations to sequester Fe from iron oxyhydroxides and silicates in the natural environment. These molecules contain hydroxamate and phenolate functional groups, and exhibit very high affinity for Fe{sup 3+}. While several studies were conducted to understand the behavior of siderophores and their application to the metal sequestration and mineral dissolution, only a few of them have examined the molecular structure of siderophores and their interactions with metals and mineral surfaces in aqueous solutions. Improved understanding of the chemical state of different functional moieties in siderophores can assist inmore » the application of these biological molecules in actinide separation, sequestration and decontamination processes. The focus of our research group is to evaluate the (a) functional group chemistry of selected siderophores and their metal complexes in aqueous solutions, and (b) the nature of siderophore interactions at the mineral-water interfaces. We selected desferrioxamine B (desB), a hydroxamate siderophore, and its small structural analogue, acetohydroxamic acid (aHa), for this investigation. We examined the functional group chemistry of these molecules as a function of pH, and their complexation with aqueous and solid phase Fe(III). For solid phase Fe, we synthesized all naturally occurring Fe(III)-oxyhydroxides (goethite, lepidocrocite, akaganeite, feroxyhite) and hematite. We also synthesized Fe-oxides (goethite and hematite) of different sizes to evaluate the influence of particle size on mineral dissolution kinetics. We used a series of molecular techniques to explore the functional group chemistry of these molecules and their complexes. Infrared spectroscopy is used to specifically identify the variations in oxime group as a function of pH and Fe(III) complexation. Resonance Raman spectroscopy was used to evaluate the nature of hydroxamate binding in the case of Fe(III)-siderophore complexes and model ligands. Soft and hard X-ray spectroscopy techniques were used to examine the electronic structure of binding groups, and their local structural environment. The synchrotron X-ray studies were conducted at the Stanford Synchrotron Radiation Laboratory and at the Advanced Light Source (Lawrence Berkeley National Laboratory). These experimental vibrational and X-ray spectroscopy studies were complemented with density functional theory calculations. The highlight of this study is the evaluation of the fundamental electronic state information of the hydroxamate moiety in siderophores during deprotonation and Fe(III) complexation. The applications of soft X-ray studies are also new, and were applied, for the first time, to examine the chemistry of organic macromolecules in aqueous solutions.« less
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NASA Astrophysics Data System (ADS)
Swartz, Christopher H.; Blute, Nicole Keon; Badruzzman, Borhan; Ali, Ashraf; Brabander, Daniel; Jay, Jenny; Besancon, James; Islam, Shafiqul; Hemond, Harold F.; Harvey, Charles F.
2004-11-01
Aquifer geochemistry was characterized at a field site in the Munshiganj district of Bangladesh where the groundwater is severely contaminated by As. Vertical profiles of aqueous and solid phase parameters were measured in a sandy deep aquifer (depth >150 m) below a thick confining clay (119 to 150 m), a sandy upper aquifer (3.5 to 119 m) above this confining layer, and a surficial clay layer (<3.5 m). In the deep aquifer and near the top of the upper aquifer, aqueous As levels are low (<10 μg/L), but aqueous As approaches a maximum of 640 μg/L at a depth of 30 to 40 m and falls to 58 μg/L near the base (107 m) of the upper aquifer. In contrast, solid phase As concentrations are uniformly low, rarely exceeding 2 μg/g in the two sandy aquifers and never exceeding 10 μg/g in the clay layers. Solid phase As is also similarly distributed among a variety of reservoirs in the deep and upper aquifer, including adsorbed As, As coprecipitated in solids leachable by mild acids and reductants, and As incorporated in silicates and other more recalcitrant phases. One notable difference among depths is that sorbed As loads, considered with respect to solid phase Fe extractable with 1 N HCl, 0.2 M oxalic acid, and a 0.5 M Ti(III)-citrate-EDTA solution, appear to be at capacity at depths where aqueous As is highest; this suggests that sorption limitations may, in part, explain the aqueous As depth profile at this site. Competition for sorption sites by silicate, phosphate, and carbonate oxyanions appear to sustain elevated aqueous As levels in the upper aquifer. Furthermore, geochemical profiles are consistent with the hypothesis that past or ongoing reductive dissolution of Fe(III) oxyhydroxides acts synergistically with competitive sorption to maintain elevated dissolved As levels in the upper aquifer. Microprobe data indicate substantial spatial comapping between As and Fe in both the upper and deep aquifer sediments, and microscopic observations reveal ubiquitous Fe coatings on most solid phases, including quartz, feldspars, and aluminosilicates. Extraction results and XRD analysis of density/magnetic separates suggest that these coatings may comprise predominantly Fe(II) and mixed valence Fe solids, although the presence of Fe(III) oxyhydroxides can not be ruled out. These data suggest As release may continue to be linked to dissolution processes targeting Fe, or Fe-rich, phases in these aquifers.
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Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.
2009-01-01
Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.
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Pink manganian phengite in a high P/ T meta-conglomerate from northern Syros (Cyclades, Greece)
NASA Astrophysics Data System (ADS)
Altherr, Rainer; Soder, Christian; Panienka, Sandra; Peters, Daniel; Meyer, Hans-Peter
2013-11-01
A new occurrence of Mn-rich rocks was discovered within the high-pressure/low-temperature metamorphic rocks on the Palos peninsula of Syros (Greece). Near the summit of Mount Príonas, a meta-conglomerate consists of calcite (~63 wt%), pink manganian phengite, blue-purple manganian aegirine-jadeite, microcline, albite and quartz. In addition, it contains abundant braunite-rich aggregates (up to ~1.5 cm in diameter) that include hollandite [(Ba0.98-1.02K<0.01Na<0.02Ca<0.03) (Mn{1.02-1.52/3+}Fe{0.38-0.88/3+}Ti0.29-0.92Mn{5.11-5.76/4+})O16], barite and manganian hematite. Due to metamorphic recrystallization and deformation, the contacts between clasts and matrix are blurred and most clasts have lost their identity. In back-scattered electron images, many aegirine-jadeite grains appear patchy and show variable jadeite contents (Jd10-67). These pyroxenes occur in contact with either quartz or albite. Manganian phengite (3.41-3.49 Si per 11 oxygen anions) is of the 3T type and contains 1.4-2.2 wt% of Mn2O3. At the known P- T conditions of high-pressure metamorphism on Syros (~1.4 GPa/ 470 °C), the mineral sub-assemblage braunite + quartz + calcite (former aragonite) suggests high oxygen fugacities relative to the HM buffer (+7 ≤ ΔfO2 ≤ + 17) and relatively high CO2 fugacities. The exact origin of the conglomerate is not known, but it is assumed that the Fe-Mn-rich and the calcite-rich particles originated from different sources. Braunite has rather low contents of Cu (~0.19 wt%) and the concentrations of Co, Ni and Zn are less than 0.09 wt%. Hollandite shows even lower concentrations of these elements. Furthermore, the bulk-rock compositions of two samples are characterized by low contents of Cu, Co and Ni, suggesting a hydrothermal origin of the manganese ore. Most likely, these Fe-Mn-Si oxyhydroxide deposits consisted of ferrihydrite, todorokite, birnessite, amorphous silica (opal-A) and nontronite. Al/(Al + Fe + Mn) ratios of 0.355 and 0.600 suggest the presence of an aluminosilicate detrital component.
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Formation of iron disilicide on amorphous silicon
NASA Astrophysics Data System (ADS)
Erlesand, U.; Östling, M.; Bodén, K.
1991-11-01
Thin films of iron disilicide, β-FeSi 2 were formed on both amorphous silicon and on crystalline silicon. The β-phase is reported to be semiconducting with a direct band-gap of about 0.85-0.89 eV. This phase is known to form via a nucleation-controlled growth process on crystalline silicon and as a consequence a rather rough silicon/silicide interface is usually formed. In order to improve the interface a bilayer structure of amorphous silicon and iron was sequentially deposited on Czochralski <111> silicon in an e-gun evaporation system. Secondary ion mass spectrometry profiling (SIMS) and scanning electron micrographs revealed an improvement of the interface sharpness. Rutherford backscattering spectrometry (RBS) and X-ray diffractiometry showed β-FeSi 2 formation already at 525°C. It was also observed that the silicide growth was diffusion-controlled, similar to what has been reported for example in the formation of NiSi 2 for the reaction of nickel on amorphous silicon. The kinetics of the FeSi 2 formation in the temperature range 525-625°C was studied by RBS and the activation energy was found to be 1.5 ± 0.1 eV.
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Tungsten solution kinetics and amorphization of nickel in mechanically alloyed Ni-W alloys
NASA Technical Reports Server (NTRS)
Aning, A. O.; Wang, Z.; Courtney, T. H.
1993-01-01
The kinetics of solution of W, and the subsequent amorphization of Ni, in mechanically alloyed Ni-W alloys has been investigated. As W is a highly abrasive material in the energy intensive devices used for mechanical alloying, we studied the above reactions in different mills. One used hardened steel balls as the grinding media, and the other Al2O3. Abrasion is common to both mills, but Fe wear debris from the hardened steel enters into solution in the Ni rich phases whereas Al2O3 debris is present as small dispersoids. The kinetics of W solution and those of subsequent amorphization do not appear strongly affected by the Fe in solution or the Al2O3 dispersoid. Tungsten dissolves in crystalline Ni in amounts in excess of the equilibrium solubility during alloying. Amorphization of the Ni phase occurs if the W content in this phase exceeds ca. 28 at. pct.
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The mobility and distribution of heavy metals during the formation of first cycle red beds.
Zielinski, R.A.; Bloch, S.; Walker, T.R.
1983-01-01
Analysis of the heavy metal content in a Holocene-Pliocene red bed sequence near San Felipe in N Baja California, Mexico, has yielded new information on the mobility and distribution of these metals during ageing of iron oxyhydroxides from the amorphous to the crystalline state. Whole-rock samples (27) and a series of successive leachates were analysed for V, Al, Cr, Mn, Fe, Co, Ni, Cu and Zn by ICP spectrometry and for U by a delayed neutron technique. These data are supported by a variety of other mineralogical and petrographical observations. The results indicate that the metal content of the samples is predominantly inherited from the constituent detrital minerals. Reddening of the whole-rock samples does not promote major open-system migration of the heavy metals; rather, contained metals redistribute themselves on an intergranular scale, moving from detrital mineral hosts to the secondary iron oxides. The amount of secondary iron oxides and the fraction of whole-rock metals associated with these oxides increase during red-bed development. In addition, the abundance of well- crystallized iron oxides increases during this period. Differences in the leaching efficiency for various metals are related to differences in metal site distribution and intergranular permeability. Inferred conditions for rapid vs limited removal of metals from red beds are summarized. It is suggested that developed red beds which are well flushed by suitable pore fluids may be sources of significant quantities of heavy metals. -J.E.S.
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NASA Astrophysics Data System (ADS)
Mladenov, N.; Kulkarni, H. V.; McKnight, D. M.; Zheng, Y.; Kirk, M. F.
2016-12-01
It was demonstrated more than two decades ago that the electron shuttling ability of fulvic acids (FA) accelerates iron (Fe) reduction. However, the environmental relevance of this mechanism for arsenic-laden groundwater environments has thus far only been hypothesized. Here we show that FAs isolated from high and low arsenic groundwater aquifers in the Bengal Basin can act to shuttle electrons between bacteria and Fe(III). Bangladesh groundwater FAs were reduced by Geobacter metallireducens and were subsequently capable of abiotically reducing Fe(III) to Fe(II). Moreover, all four Bangladesh groundwater FAs investigated in the study had higher Fe(III) to Fe(II) conversion rates compared to anthraquinone disulfonate, an oxidized quinone, and Suwannee River Fulvic Acid, a commercially-available FA isolated from a terrestrially-dominated surface water source. Until now, microbially-mediated reductive dissolution of Fe (oxy)hydroxides, driven by the availability of labile organic matter, was widely accepted as the main control on arsenic mobilization in reducing aquifers. Our evidence for the electron shuttling ability of Bangladesh FAs implicates electron shuttling as another important control on elevated As concentrations in groundwater of the Bengal Basin.
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Lipfert, G.; Reeve, A.S.; Sidle, W.C.; Marvinney, R.
2006-01-01
High mean As concentrations of up to 26.6 ??mol/L (1990 ??g/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 ??mol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO 3 type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO3 type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO3 and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO4 concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions. Crown Copyright ?? 2006 Published by Elsevier Ltd. All rights reserved.
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Beyond clay - using selective extractions to improve predictions of soil carbon content
NASA Astrophysics Data System (ADS)
Rasmussen, C.; Berhe, A. A.; Blankinship, J. C.; Crow, S. E.; Druhan, J. L.; Heckman, K. A.; Keiluweit, M.; Lawrence, C. R.; Marin-Spiotta, E.; Plante, A. F.; Schaedel, C.; Schimel, J.; Sierra, C. A.; Thompson, A.; Wagai, R.; Wieder, W. R.
2016-12-01
A central component of modern soil carbon (C) models is the use of clay content to scale the relative partitioning of decomposing plant material to respiration and mineral stabilized soil C. However, numerous pedon to plot scale studies indicate that other soil mineral parameters, such as Fe- or Al-oxyhydroxide content and specific surface area, may be more effective than clay alone for predicting soil C content and stabilization. Here we directly address the following question: Are there soil physicochemical parameters that represent mineral C association and soil C content that can replace or be used in conjunction with clay content as scalars in soil C models. We explored the relationship of soil C content to a number of soil physicochemical and physiographic parameters using the National Cooperative Soil Survey database that contains horizon level data for > 62,000 pedons spanning global ecoregions and geographic areas. The data indicated significant variation in the degree of correlation among soil C, clay and Fe-/Al-oxyhydroxides with increasing moisture variability. Specifically, dry, water-limited systems (PET/MAP > 1) presented strong positive correlations between clay and soil C, that decreased significantly to little or no correlation in wet, energy-limited systems (PET/MAP < 1). In contrast, the correlation of soil C to oxalate extractable Al+Fe increased significantly with increasing moisture availability. This pattern was particularly well expressed for subsurface B horizons. Multivariate analyses indicated similar patterns, with clear climate and ecosystem level variation in the degree of correlation among soil C and soil physicochemical properties. The results indicate a need to modify current soil C models to incorporate additional C partitioning parameters that better account for climate and ecoregion variability in C stabilization mechanisms.
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Aronhime, Natan; Zoghlin, Eli; Keylin, Vladimir; ...
2017-09-26
Fe-Ni based metal amorphous nanocomposites (MANCs) are investigated in the pseudo-binary alloys (Fe 100–xNi x) 80Nb 4Si 2B 14. To optimize the soft magnetic properties of the nanocomposites, primary and secondary crystallization kinetics must be understood. As such, primary and secondary crystallization temperatures are determined by differential scanning calorimetry, and activation energies are calculated, along with the resulting crystalline phases. Time-temperature-transformation diagrams for primary and secondary crystallization in (Fe 70Ni 30) 80Nb 4Si 2B 14 are presented. Saturation magnetization and Curie temperature are determined. In conclusion, the shape of magnetization vs. time curves for (Fe 30Ni 70) 80Nb 4Si 2Bmore » 14 at various temperatures suggest that the secondary crystal product often consumes some of the primary crystalline product.« less
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Effect of Y addition on crystallization behavior and soft-magnetic properties of Fe78Si9B13 ribbons
NASA Astrophysics Data System (ADS)
Zhanwei, Liu; Dunbo, Yu; Kuoshe, Li; Yang, Luo; Chao, Yuan; Zilong, Wang; Liang, Sun; Kuo, Men
2017-08-01
A series of amorphous Fe-Si-B ribbons with various Y addition were prepared by melt-spinning. The effect of Y addition on crystallization behavior, thermal and magnetic properties was systematically investigated. With the increase of Y content, the initial crystallization temperature shifted to a higher temperature, indicating that the thermal stability of amorphous state in Fe-Si-B-Y ribbon is enhanced compared to that of Fe-Si-B alloy. Meanwhile, compared to the two exothermic peaks in the samples with lower Y content, a new exothermic peak was found in the ribbons with Y content higher than 1 at%, which corresponded to the decomposition of metastable Fe3B phase. Among all the alloys, Fe76.5Si9B13Y1.5 alloy exhibits optimized magnetic properties, with high saturation magnetization Ms of 187 emu/g and low coercivity HcJ of 7.6 A/m.
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Xie, Wenhe; Li, Suyuan; Wang, Suiyan; Xue, Song; Liu, Zhengjiao; Jiang, Xinyu; He, Deyan
2014-11-26
N-doped amorphous carbon coated Fe3O4/SnO2 coaxial nanofibers were prepared via a facile approach. The core composite nanofibers were first made by electrospinning technology, then the shells were conformally coated using the chemical bath deposition and subsequent carbonization with polydopamine as a carbon source. When applied as a binder-free self-supported anode for lithium ion batteries, the coaxial nanofibers displayed an enhanced electrochemical storage capacity and excellent rate performance. The morphology of the interwoven nanofibers was maintained even after the rate cycle test. The superior electrochemical performance originates in the structural stability of the N-doped amorphous carbon shells formed by carbonizing polydopamine.
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NASA Astrophysics Data System (ADS)
Shang, Xiao; Yan, Kai-Li; Lu, Shan-Shan; Dong, Bin; Gao, Wen-Kun; Chi, Jing-Qi; Liu, Zi-Zhang; Chai, Yong-Ming; Liu, Chen-Guang
2017-09-01
Developing cost-effective electrocatalysts with both high activity and stability remains challenging for oxygen evolution reaction (OER) in water electrolysis. Herein, based on V-doped nickel sulfide nanowire on nickel foam (NiVS/NF), we further conduct controllable electrodeposition of Fe hydroxides film on NiVS/NF (eFe/NiVS/NF) to further improve OER performance and stability. For comparison, ultrafast chemical deposition of Fe hydroxides on NiVS/NF (uFe/NiVS/NF) is also utilized. V-doping of NiVS/NF may introduce more active sites for OER, and nanowire structure can expose abundant active sites and facilitate mass transport. Both of the two depositions generate amorphous Fe hydroxides film covering on the surface of nanowires and lead to enhanced OER activities. Furthermore, electrodeposition strategy realizes uniform Fe hydroxides film on eFe/NiVS/NF confirmed by superior OER activity of eFe/NiVS/NF than uFe/NiVS/NF with relatively enhanced stability. The OER activity of eFe/NiVS/NF depends on various electrodepositon time, and the optimal time (15 s) is obtained with maximum OER activity. Therefore, the controllable electrodeposition of Fe may provide an efficient and simple strategy to enhance the OER properties of electrocatalysts.
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NASA Astrophysics Data System (ADS)
Wegorzewski, A.; Webb, S.; Grangeon, S.; Kuhn, T.
2016-12-01
Mn-nodules are Mn-Fe (oxy)hydroxides bearing high amounts of economically important metals such as Ni, Cu, Co, Mo, as well as high field strength elements. According to that nodules are interesting for science and industry. Especially the sorption sites of metals (Ni, Cu, Mo) by the mineral phases are important to understand their coordination environment and further to tailor a specific metallurgical treatment in order to optimize the metal extraction procedure. Nodules used for this study were sampled from the German license area within the Clarion Clipperton Zone in the Pacific. These nodules grow on the seafloor in 4200 m depth by metal precipitation from oxic (hydrogenetic growth) and/or suboxic waters (suboxic diagenetic growth; Halbach et al., 1988). They show a complex texture characterized by irregular, concentrically banded nm- to µm-thick layered growth structures (LGS). Electronmicroprobe and X-ray diffraction analyses reveal: suboxic diagenetic LGS have high Mn/Fe ratios (9-826; Mn ≈ 40 wt. %; Fe ≈ 0.5 wt %), high Ni (0.3-2.6 wt %) and Cu (0.5-3.0 wt %) contents but low Co content (0.02±0.01 wt %). Mineralogically those LGS are turbostratic phyllomanganates (vernadite), which consist of [MnO6]-octahedral layers, separated from each other by cations (e.g., Na, Mg) and water in the interlayer, forming 7 and 10 Å phyllomanganates (Bode et al., 2007). In contrast hydrogenetic LGS show low Mn/Fe ratios (<5), low Ni+Cu content (<1 wt%) but enrichment in Co (≤0.5 wt%). Those LGS are of δ-MnO2, which is epitaxially intergrown with an amorphous FeOOH phase. In general, phyllomanganates have a high opportunity to incorporate metals due to their negative layer charge deficit cause by abundant isomorphic substitution of Mn4+ by Mn3+ and vacancies within MnO2 sheets. The negative charge deficit can be balanced by hydrated interlayer cations (e.g., Na, Mg) or due to metals adsorption at cation vacancy sites, incorporation into the MnO2 sheet and/or adsorption at lateral edge surfaces (Peacock, 2009; Pena et al., 2015). A special emphasis of this study was to determine the boundings of Ni, Cu, Co and Mo by the Mn-mineral phases of nodules. X-ray absorption spectroscopy analyses show that metals such as Ni, Cu, Co are rather incorporated into MnO2 sheets than adsorbed as inner-sphere complexes over/below vacancies, like Mo.
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Induced anisotropy in FeCo-based nanocomposites: Early transition metal content dependence
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shen, S; DeGeorge, V; Ohodnicki, PR
2014-05-07
Soft magnetic nanocomposites variants of FeCo-based (HTX002) alloys (Fe65Co35)(81+x)B12Nb4-xSi2Cu1, exhibiting high inductions (up to 1.9 T), low losses, and high temperature stability are studied for high frequency inductors and current sensors. For alloys with x 0, 1, 1.5, 2, and 3, we report field induced anisotropy, K-U, after annealing at temperatures of 340-450 degrees C for 1 h in a 2 T transverse magnetic field. The anisotropy field, H-K, measured by AC permeametry on toroidal cores, and by first order reversal curves on square sections of ribbon, decreases with annealing temperature and saturates at high annealing temperatures suggesting a nanostructuremore » related anisotropy mechanism in which the amorphous phase exhibits a higher H-K than the crystalline phase. A high saturation induction nanocrystalline phase and high H-K amorphous phase were achieved by low temperature annealing resulting in a value of K-U exceeding 14 X 10(3) erg/cm(3), more than twice that reported previously for Fe-rich amorphous and nanocomposite alloys. (C) 2014 AIP Publishing LLC.« less
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Structure and soft magnetic properties of Fe-Si-B-P-Cu nanocrystalline alloys with minor Mn addition
NASA Astrophysics Data System (ADS)
Jia, Xingjie; Li, Yanhui; Wu, Licheng; Zhang, Wei
2018-05-01
Addition of minor Mn effectively improves the amorphous-forming ability and thermal stability of the Fe85Si2B8P4Cu1 alloy. With increasing the Mn content from 0 to 3 at.%, the critical thickness for amorphous formation and onset temperature of the primary crystallization increase from 14 μm and 659 K to 27 μm and 668 K, respectively. The fine nanocrystalline structure with α-Fe grains in size (D) of < 20 nm was obtained for the annealed amorphous alloys, which show excellent soft magnetic properties. The alloying of Mn reduces the coercivity (Hc) by decreasing the D value and widens the optimum annealing temperature range for obtaining low Hc, although the saturation magnetic flux density (Bs) is decreased slightly. The Fe83Mn2Si2B8P4Cu1 nanocrystalline alloy possesses fine structure with a D of ˜17.5 nm, and exhibits a high Bs of ˜1.75 T and a low Hc of ˜5.9 A/m. The mechanism related to the alloying effects on the structure and magnetic properties was discussed in term of the crystallization activation energy.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jeon, Seong-Jae, E-mail: jsjigst@ecei.tohoku.ac.jp; Saito, Shin; Hinata, Shintaro
Effect of bcc Cr{sub 80}Mn{sub 20} seed layer and Cr{sub 50}Ti{sub 50} amorphous texture inducing layer on the heteroepitaxy system in FePt-C granular film was studied by introducing a new concept of the layered structure. The concept suggested that the large grain seed layer in which the crystallographic texture was initially formed on an amorphous layer in the layered structure can reduce the angular distribution of (002) c-axis crystal orientation in the FePt-C granular film owing to heteroepitaxial growth. Structure analysis by X-ray diffraction revealed that (1) when the substrate heating temperature was elevated from 300 °C to 500 °C, grain sizemore » in the seed layer increased from 9.8 nm to 11.6 nm, and then decreased with further increasing the substrate temperature. The reduction of the grain size over 500 °C corresponds to the crystallization of the amorphous texture inducing layer, (2) when the grain size increased from 9.8 nm to 11.6 nm, the angular distribution of the (002) orientation in the seed layer dramatically decreased from 13.7° to 4.1°. It was shown that the large grain seed layer increased the perpendicular hysteresis in FePt-C granular film.« less
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Dean, W.E.; Doner, L.A.
2012-01-01
Little Shingobee Lake and Fen are part of the extensive network of lakes and wetlands in the Shingobee River headwaters of northwestern Minnesota, designed to study the interactions between surface and ground waters. Prior to about 11. 2 cal. ka, most of these lakes and wetlands were interconnected to form glacial Lake Willobee, which apparently formed when a debris flow dammed the Shingobee River. Between 11. 2 and 8. 5 cal. ka, the level of Lake Willobee fell as a result of breaching of the dam, transforming the deep lake into the existing lakes and wetlands. Analyses of a 9-m core from Little Shingobee Lake (LSL-B), and lacustrine sediments under 3. 3 m of peat in a 17-m core from Little Shingobee Fen (LSF-10), show that the dominant components are allogenic clastic material, and endogenic CaCO3 and organic matter. In both cores almost all of the iron (Fe) and manganese (Mn) are incorporated in endogenic minerals, presumed to be X-ray amorphous oxyhydroxide minerals, that occur in significant quantities throughout the cores; almost no Fe and Mn are contributed from detrital aluminosilicate minerals. This suggests that, for most of the Holocene, the allogenic watershed contributions to lake chemistry were minor compared to the dissolved mineral load. In addition, prior to 3. 5 cal. ka, pollen zone boundaries coincide with large changes in lake-sediment mineralogy, indicating that both landscape and climate processes were linked to early- and mid-Holocene lake chemistry. The pollen time series, with sequential domination by spruce, pine, sagebrush-oak, birch-oak and, finally, white pine is typical of the region and reflects the changing location of the prairie-forest transition zone over time. These changes in vegetation had some profound effects on the geochemistry of the lake waters. ?? 2011 Springer Science+Business Media B.V. (outside the USA).
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NASA Technical Reports Server (NTRS)
Shogrin, Bradley; Jones, William R., Jr.; Wilbur, Paul J.; Pilar, Herrera-Fierro; Williamson, Don L.
1995-01-01
The lubricating lifetime of thin films of a perfluoropolyether (PFPE) based on hexafluoropropene oxide in the presence of ion implanted 440C stainless steel is presented. Stainless steel discs, either unimplanted or implanted with N2, C, Ti, Ti + N2, or Ti + C had a thin film of PFPE (60-400 A) applied to them reproducibly (+/- 20 percent) and uniformly (+/- 15 percent) using a device developed for this study. The lifetimes of these films were quantified by measuring the number of sliding-wear cycles required to induce an increase in the friction coefficient from an initial value characteristic of the lubricated wear couple to a final, or failure value, characteristic of an unlubricated, unimplanted couple. The tests were performed in a dry nitrogen atmosphere (less than 1 percent RH) at room temperature using a 3 N normal load with a relative sliding speed of 0.05 m/s. The lubricated lifetime of the 440C couple was increased by an order of magnitude by implanting the disc with Ti. Ranked from most to least effective, the implanted species were: Ti; Ti+C; unimplanted; N2; C approximately equals Ti+N2. The mechanism postulated to explain these results involves the formation of a passivating or reactive layer which inhibits or facilitates the production of active sites. The corresponding surface microstructures induced by ion implantation, obtained using x-ray diffraction and conversion electron Mossbauer spectroscopy, ranked from most to least effective in enhancing lubricant lifetime were: amorphous Fe-Cr-Ti; amorphous Fe-Cr-Ti-C + TiC; unimplanted; epsilon-(Fe,Cr)(sub x)N, x = 2 or 3; amorphous Fe-Cr-C approximately equals amorphous Fe-Cr-Ti-N.
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Laboratory studies of refractory metal oxide smokes
NASA Technical Reports Server (NTRS)
Nuth, Joseph A.; Nelson, R. N.; Donn, Bertram
1989-01-01
Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.
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Effects of annealing on the structure and magnetic properties of Fe80B20 magnetostrictive fibers.
Zhu, Qianke; Zhang, Shuling; Geng, Guihong; Li, Qiushu; Zhang, Kewei; Zhang, Lin
2016-07-04
Fe80B20 amorphous alloys exhibit excellent soft magnetic properties, high abrasive resistance and outstanding corrosion resistance. In this work, Fe80B20 amorphous micro-fibers with HC of 3.33 Oe were firstly fabricated and the effects of annealing temperature on the structure and magnetic properties of the fibers were investigated. In this study, Fe80B20 amorphous fibers were prepared by the single roller melt-spinning method. The structures of as-spun and annealed fibers were investigated by X-ray diffractometer (XRD) (PANalytical X,Pert Power) using Cu Kα radiation. The morphology of the fibers was observed by scanning electron microscopy (SEM) (HITACHI-S4800). Differential scanning calorimetry (DSC) measurements of the fibers were performed on Mettler Toledo TGA/DSC1 device under N2 protection. Vibrating sample magnetometer (VSM, Versalab) was used to examine the magnetic properties of the fibers. The resonance behavior of the fibers was characterized by an impedance analyzer (Agilent 4294A) with a home-made copper coil. The X-ray diffusion (XRD) patterns show that the fibers remain amorphous structure until the annealing temperature reaches 500°C. The differential scanning calorimetry (DSC) results show that the crystallization temperature of the fibers is 449°C. The crystallization activation energy is calculated to be 221 kJ/mol using Kissinger formula. The scanning electron microscopy (SEM) images show that a few dendrites appear at the fiber surface after annealing. The result indicates that the coercivity HC (//) and HC (⊥) slightly increases with increasing annealing temperature until 400°C, and then dramatically increases with further increasing annealing temperature which is due to significant increase in magneto-crystalline anisotropy and magneto-elastic anisotropy. The Q value firstly increases slightly when the annealing temperature rises from room temperature (RT) to 300°C, then decreases until 400°C. Eventually, the value of Q increases to ~2000 at annealing temperature of 500°C. In this study, Fe80B20 amorphous fibers with the diameter of 60 μm were prepared by the single roller melt-spinning method and annealed at 200°C, 300°C, 400°C, and 500°C, respectively. XRD results indicate that the fiber structure remains amorphous when the annealing temperature is below 400°C. α-Fe phase and Fe3B phase appear when the annealing temperature rises to 500°C, which is above the crystallization temperature of 449°C. The recrystallization activation energy is calculated to be 221 kJ/mol. The coercivity increases with increasing annealing temperature, which attributes to the increase of total anisotropy. All the as-spun and annealed fibers exhibit good resonance behavior for magnetostrictive sensors.
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NASA Astrophysics Data System (ADS)
Wang, Wen; Li, Boyu; Zhai, Sicheng; Xu, Juan; Niu, Zuozhe; Xu, Jing; Wang, Yan
2018-02-01
In this paper, FeSiBAlNiCo x (x = 0.2, 0.8) high-entropy alloy (HEA) powders were fabricated by mechanical alloying process, and the powders milled for 140 h were sintered by spark plasma sintering (SPS) technique. The microstructures and properties of as-milled powders and as-sintered samples were investigated. The results reveal that the final milling products (140 h) of both sample powders present the fully amorphous structure. The increased Co contents obviously enhance the glass forming ability and thermal stability of amorphous HEA powders, which are reflected by the shorter formation time of fully amorphous phase and the higher onset crystallization temperature, respectively. According to coercivity, the as-milled FeSiBAlNiCo x (x = 0.2, 0.8) powders (140 h) are the semi-hard magnetic materials. FeSiBAlNiCo0.8 HEA powders possess the highest saturation magnetization and largest remanence ratio. The SPS-ed products of both bulk HEAs are composed of body-centered cubic solid solution, and FeSi and FeB intermetallic phases. They possess the high relative density above 97% and excellent microhardness exceeding 1150 HV. The as-sintered bulks undergo the remarkable increase in saturation magnetization compared with the as-milled state. The SPS-ed FeSiBAlNiCo0.8 HEA exhibits the soft magnetic properties. The electrochemical corrosion test is carried out in 3.5% NaCl solution. The SPS-ed FeSiBAlNiCo0.2 HEA reveals the better passivity with low passive current density, and the higher pitting resistance with wide passive region.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Dwivedi, Jagrati, E-mail: jdwivedi.phy@gmail.com; Mishra, Ashutosh; Gupta, Ranjeeta
2016-05-23
Structural changes occurring in a thin amorphous Co{sub 23}Fe{sub 60}B{sub 17} film sandwiched between two Mo layers, as a function of thermal annealing has been studied. Thermal stability of the Co{sub 23}Fe{sub 60}B{sub 17} film is found to be significantly lower than the bulk ribbons. SIMS measurements show that during crystallization, boron which is expelled out of the crystallites, has a tendency to move towards the surface. No significant diffusion of boron in Mo buffer layer is observed. This result is in contrast with some earlier studies where it was proposed that the role of buffer layer of refractory metalmore » is to absorb boron which is expelled out of the bcc FeCo phase during crystallization.« less
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Magnetic moment arrangement in amorphous Fe 0.66Er 0.19B 0.15
NASA Astrophysics Data System (ADS)
Szymański, K.; Kalska, B.; Satuła, D.; Dobrzyński, L.; Broddefalk, A.; Wäppling, R.; Nordblad, P.
2002-11-01
Magnetization measurements and Mössbauer spectroscopy with and without a monochromatic circularly polarized Mössbauer source (MCPMS) have been performed in order to determine the magnetic properties of the amorphous alloy Fe 0.66Er 0.19B 0.15. The system is found to order ferrimagnetically at TC=330 K and to show a compensation temperature ( Tcomp) at 120 K. A reorientation of the magnetic moments of iron and erbium during sample cooling through the compensation point in magnetic field is clearly displayed in the MCPMS data. The orientation of the net magnetic moment is due to the orientation of Fe moments above Tcomp and to Er moments at low temperatures. The results are compatible with a model of predominantly antiferromagnetic Fe-Er coupling accompanied by random local anisotropy acting on the Er moments.
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Linking Thermodynamics to Pollutant Reduction Kinetics by Fe2+ Bound to Iron Oxides.
Stewart, Sydney M; Hofstetter, Thomas B; Joshi, Prachi; Gorski, Christopher A
2018-05-15
Numerous studies have reported that pollutant reduction rates by ferrous iron (Fe 2+ ) are substantially enhanced in the presence of an iron (oxyhydr)oxide mineral. Developing a thermodynamic framework to explain this phenomenon has been historically difficult due to challenges in quantifying reduction potential ( E H ) values for oxide-bound Fe 2+ species. Recently, our group demonstrated that E H values for hematite- and goethite-bound Fe 2+ can be accurately calculated using Gibbs free energy of formation values. Here, we tested if calculated E H values for oxide-bound Fe 2+ could be used to develop a free energy relationship capable of describing variations in reduction rate constants of substituted nitrobenzenes, a class of model pollutants that contain reducible aromatic nitro groups, using data collected here and compiled from the literature. All the data could be described by a single linear relationship between the logarithms of the surface-area-normalized rate constant ( k SA ) values and E H and pH values [log( k SA ) = - E H /0.059 V - pH + 3.42]. This framework provides mechanistic insights into how the thermodynamic favorability of electron transfer from oxide-bound Fe 2+ relates to redox reaction kinetics.
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The Effect of Spatial Heterogeneities on Nucleation Kinetics in Amorphous Aluminum Alloys
NASA Astrophysics Data System (ADS)
Shen, Ye
The mechanical property of the Al based metallic glass could be enhanced significantly by introducing the high number density of Al-fcc nanocrystals (1021 ˜1023 m-3) to the amorphous matrix through annealing treatments, which motivates the study of the nucleation kinetics for the microstructure control. With the presence of a high number density (1025 m-3) of aluminum-like medium range order (MRO), the Al-Y-Fe metallic glass is considered to be spatially heterogeneous. Combining the classical nucleation theory with the structural configuration, a MRO seeded nucleation model has been proposed and yields theoretical steady state nucleation rates consistent with the experimental results. In addition, this model satisfies all the thermodynamic and kinetic constraints to be reasonable. Compared with the Al-Y-Fe system, the primary crystallization onset temperature decreases significantly and the transient delay time (tau) is shorter in the Al-Y-Fe-Pb(In) systems because the insoluble Pb and In nanoparticles in the amorphous matrix served as extrinsic spatial heterogeneity to provide the nucleation sites for Al-fcc precipitation and the high-resolution transmission electron microscopy (HRTEM) images of the Pb-Al interface revealed a good wetting behavior between the Al and Pb nanoparticles. The study of the transient delay time (tau) could provide insight on the transport behavior during the nucleation and a more convenient approach to evaluate the delay time has been developed by measuring the Al-Y-Fe amorphous alloy glass transition temperature (Tg) shift with the increasing annealing time (tannealing) in FlashDSC. The break point in the Tg vs. log(tannealing) plot has been identified to correspond to the delay time by the TEM characterization. FlashDSC tests with different heating rates and different compositions (Al-Y-Fe-Pb and Zn-Mg-Ca-Yb amorphous alloys) further confirmed the break point and delay time relationship. The amorphous matrix composition and the enthalpy analysis indicates that there are different mechanisms leading to the Tg shift before and after the break point. Before the break point, Tg shifts solely due to the increased glass stability through a relaxation process. However, after the break point, Tg shifts to higher temperatures because of both the relaxation and the composition change effects.
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O'Reilly, S Erin; Watkins, Janet; Furukawa, Yoko
2005-01-01
Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III) respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III).
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Dippon, Urs; Pantke, Claudia; Porsch, Katharina; Larese-Casanova, Phil; Kappler, Andreas
2012-06-19
The mobility of toxic metals and the transformation of organic pollutants in the environment are influenced and in many cases even controlled by iron minerals. Therefore knowing the factors influencing iron mineral formation and transformation by Fe(II)-oxidizing and Fe(III)-reducing bacteria is crucial for understanding the fate of contaminants and for the development of remediation technologies. In this study we followed mineral formation by the nitrate-reducing Fe(II)-oxidizing strain Acidovorax sp. BoFeN1 in the presence of the crystalline Fe(III) (oxyhydr)oxides goethite, magnetite and hematite added as potential nucleation sites. Mössbauer spectroscopy analysis of minerals precipitated by BoFeN1 in (57)Fe(II)-spiked microbial growth medium showed that goethite was formed in the absence of mineral additions as well as in the presence of goethite or hematite. The presence of magnetite minerals during Fe(II) oxidation induced the formation of magnetite in addition to goethite, while the addition of humic substances along with magnetite also led to goethite but no magnetite. This study showed that mineral formation not only depends on the aqueous geochemical conditions but can also be affected by the presence of mineral nucleation sites that initiate precipitation of the same underlying mineral phases.
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Recoil-free Fraction in Amorphous and Nanocrystalline Aluminium Based Alloys
NASA Astrophysics Data System (ADS)
Sitek, Jozef
2008-10-01
Aluminium based rapidly quenched alloys of nominal composition Al90Fe7Nb3 and Al94Fe2V4 were studied by Mössbauer spectroscopy. We have measured the recoil-free fraction and thermal shift at room and liquid nitrogen temperature. The frequency modes of atomic vibrations were determined and consequently the characteristic Debye temperature was derived. Characteristic temperature calculated from f-factor was lower than those fitted from second order Doppler shift. This indicates the presence of different frequency modes for amorphous and nanocrystalline states.
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NASA Technical Reports Server (NTRS)
Ralston, S. J.; Hausrath, E. M.; Tschauner, O.; Rampe, E. B.; Christoffersen, R.
2018-01-01
Investigations with the CheMin Xray Diffractometer (XRD) onboard the Curiosity rover in Gale Crater demonstrate that all rock and soil samples measured to date contain approximately 15-70 weight percentage X-ray amorphous materials. The diffuse scattering hump from the X-ray amorphous materials in CheMin XRD patterns can be fit with a combination of allophane, ferrihydrite, and rhyolitic and basaltic glass. Because of the iron-rich nature of Mars' surface, Fe-rich poorly-crystalline phases, such as hisingerite, may be present in addition to allophane.
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Zhu, Changbao; Mu, Xiaoke; Popovic, Jelena; Weichert, Katja; van Aken, Peter A; Yu, Yan; Maier, Joachim
2014-09-10
Much attention has been paid to metastable materials in the lithium battery field, especially to nanocrystalline and amorphous materials. Nonetheless, fundamental issues such as lithium potential variations have not been pertinently addressed. Using LiFePO4 as a model system, we inspect such lithium potential variations for various lithium storage modes and evaluate them thermodynamically. The conclusions of this work are essential for an adequate understanding of the behavior of electrode materials and even helpful in the search for new energy materials.
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NASA Astrophysics Data System (ADS)
Ziemian, Constance W.; Wright, Wendelin J.; Cipoletti, David E.
2018-05-01
Cold spray is a promising method by which to deposit dense Fe-based metallic glass coatings on conventional metal substrates. Relatively low process temperatures offer the potential to prevent the crystallization of amorphous feedstock powders while still providing adequate particle softening for bonding and coating formation. In this study, Fe48Mo14Cr15Y2C15B6 powder was sprayed onto a mild steel substrate, using a variety of process conditions, to investigate the feasibility of forming well-bonded amorphous Fe-based coatings. Particle splat adhesion was examined relative to impact conditions, and the limiting values of temperature and velocity associated with successful softening and adhesion were empirically established. Variability of particle sizes, impact temperatures, and impact velocities resulted in splat morphologies ranging from well-adhered deformed particles to substrate craters formed by rebounded particles and a variety of particle/substrate interface conditions. Transmission electron microscopy studies revealed the presence of a thin oxide layer between well-adhered particles and the substrate, suggesting that bonding is feasible even with an increased oxygen content at the interface. Results indicate that the proper optimization of cold spray process parameters supports the formation of Fe-based metallic glass coatings that successfully retain their amorphous structure, as well as the superior corrosion and wear-resistant properties of the feedstock powder.
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EFFECT OF PRE-ALLOYING CONDITION ON THE BULK AMORPHOUS ALLOY ND(60)FE(30)AL(10).
DOE Office of Scientific and Technical Information (OSTI.GOV)
OCONNOR,A.S.; LEWIS,L.H.; MCCALLUM,R.W.
Bulk metallic glasses are materials that require only modest cooling rates to obtain amorphous solids directly from the melt. Nd{sub 60}Fe{sub 30}Al{sub 10} has been reported to be a ferromagnetic bulk metallic glass that exhibits high coercivity, a combination unlike conventional Nd-based amorphous magnetic alloys. To clarify the relationship between short-range order and high coercivity in glassy Nd{sub 60}Fe{sub 30}Al{sub 10}, experiments were performed to verify the existence of a homogeneous liquid state prior to rapid solidification. Alloys were prepared by various pre-alloying routes and then melt-spun. Arc-melted alloys were prepared for melt spinning using three different protocols involving: (1)more » alloying all three elements at once, (2) forming a Nd-Fe alloy which was subsequently alloyed with Al, and (3) forming a Fe-Al alloy for subsequent alloying with Nd. XRD, DTA, and magnetic measurement data from the resultant ribbons indicate significant differences in both the glassy fraction and the crystalline phase present in the as-spun material. These observed differences are attributed to the presence of highly stable nanoscopic aluminide-and/or silicide-phases, or motes, present in the melt prior to solidification. These motes would affect the short-range order and coercivity of the resultant glassy state and are anticipated to provide heterogeneous nucleation sites for crystallization.« less
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A novel Fe(II)-oxidizing Epsilonproteobacterium from a streambank aquifer
NASA Astrophysics Data System (ADS)
Chan, C. S.; McAllister, S.; Krepski, S.; Lin, C.; Lazareva, O.; Kan, J.
2013-12-01
Neutrophilic Fe(II)-oxidizing microorganisms (FeOM) play significant roles in elemental cycling in freshwater environments, forming biogenic Fe(III)-oxyhydroxides that sorb and sequester organics, phosphate, heavy metals, and other solutes. However, the extent of these microbes' diversity and influence are unknown, in part because we may only recognize a fraction of FeOM in environmental settings. Here we describe the first known Fe(II)-oxidizing Epsilonproteobacterium, Sulfuricurvum sp. strain EW, isolated from a biogeochemically dynamic streambank aquifer in southeastern Pennsylvania. This strain is related to the sulfur-oxidizer Sulfuricurvum kujiense (98.3% small subunit rRNA gene sequence identity). Strain EW is a facultative FeOM, capable of aerobically oxidizing reduced sulfur compounds, hydrogen, and a number of organic substrates. Pyrosequencing of the SSU rRNA gene (V1-V3 region) from porewater samples shows that Sulfuricurvum spp. is concentrated in an Fe- and organic-rich stratum within the streambank. Over the course of a year, the temporal patterns are similar to Gallionellaceae, a family with isolates that are almost exclusively FeOM. Correlation with geochemical parameters suggest that Sulfuricurvum presence is controlled by conditions favorable for Fe oxidation. These results significantly increase the known distribution, diversity, and physiology of FeOM, enabling further discoveries on the mechanisms and effects of microbial Fe oxidation. Although Epsilonproteobacteria have previously been associated with H2, S, and organic metabolisms, this discovery opens the door to understanding their roles in environmental Fe cycling.
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Muehe, E Marie; Adaktylou, Irini J; Obst, Martin; Zeitvogel, Fabian; Behrens, Sebastian; Planer-Friedrich, Britta; Kraemer, Ute; Kappler, Andreas
2013-01-01
Cadmium (Cd) is of environmental relevance as it enters soils via Cd-containing phosphate fertilizers and endangers human health when taken up by crops. Cd is known to associate with Fe(III) (oxyhydr)oxides in pH-neutral to slightly acidic soils, though it is not well understood how the interrelation of Fe and Cd changes under Fe(III)-reducing conditions. Therefore, we investigated how the mobility of Cd changes when a Cd-bearing soil is faced with organic carbon input and reducing conditions. Using fatty acid profiles and quantitative PCR, we found that both fermenting and Fe(III)-reducing bacteria were stimulated by organic carbon-rich conditions, leading to significant Fe(III) reduction. The reduction of Fe(III) minerals was accompanied by increasing soil pH, increasing dissolved inorganic carbon, and decreasing Cd mobility. SEM-EDX mapping of soil particles showed that a minor fraction of Cd was transferred to Ca- and S-bearing minerals, probably carbonates and sulfides. Most of the Cd, however, correlated with a secondary iron mineral phase that was formed during microbial Fe(III) mineral reduction and contained mostly Fe, suggesting an iron oxide mineral such as magnetite (Fe3O4). Our data thus provide evidence that secondary Fe(II) and Fe(II)/Fe(III) mixed minerals could be a sink for Cd in soils under reducing conditions, thus decreasing the mobility of Cd in the soil.
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NASA Technical Reports Server (NTRS)
Miyoshi, K.; Buckley, D. H.
1984-01-01
Friction and wear tests were conducted with 3.2- and 6.4-millimeter-diameter aluminum oxide spheres sliding, in reciprocating motion, on a Fe67Co18B14Si1 metallic foil. Crystallites with a size range of 10 to 150 nanometers were produced on the wear surface of the amorphous alloy. A strong interaction between transition metals and metalloids such as silicon and boron results in strong segregation during repeated sliding, provides preferential transition metal-metalloid clustering in the amorphous alloy, and subsequently produces the diffused honeycomb structure formed by dark grey bands and primary crystals, that is, alpha-Fe in the matrix. Large plastic flow occurs on an amorphous alloy surface with sliding and the flow film of the alloy transfers to the aluminum oxide pin surface. Multiple slip bands due to shear deformation are observed on the side of the wear track. Two distinct types of wear debris were observed as a result of sliding: an alloy wear debris, and/or powdery-whiskery oxide debris.
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NASA Astrophysics Data System (ADS)
Wei, Ran; Sun, Huan; Chen, Chen; Tao, Juan; Li, Fushan
2018-03-01
Fe-Co-Ni-Si-B high entropy amorphous alloys composites (HEAACs), which containing high entropy solid solution phase in amorphous matrix, show good soft magnetic properties and bending ductility even in optimal annealed state, were successfully developed by melt spinning method. The crystallization phase of the HEAACs is solid solution phase with body centered cubic (BCC) structure instead of brittle intermetallic phase. In addition, the BCC phase can transformed into face centered cubic (FCC) phase with temperature rise. Accordingly, Fe-Co-Ni-Si-B high entropy alloys (HEAs) with FCC structure and a small amount of BCC phase was prepared by copper mold casting method. The HEAs exhibit high yield strength (about 1200 MPa) and good plastic strain (about 18%). Meanwhile, soft magnetic characteristics of the HEAs are largely reserved from HEAACs. This work provides a new strategy to overcome the annealing induced brittleness of amorphous alloys and design new advanced materials with excellent comprehensive properties.
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NASA Astrophysics Data System (ADS)
Li, Ruifeng; Li, Zhuguo; Huang, Jian; Zhu, Yanyan
2012-08-01
Ni-Fe-B-Si-Nb coatings have been deposited on mild steel substrates using high power diode laser cladding. Scanning laser beam at high speeds was followed to remelt the surface of the coatings. Different laser cladding powers in the range of 700-1000 W were used to obtain various dilution ratios in the coating. The dilution effect on the chemical characterization, phase composition and microstructure is analyzed by energy dispersive spectroscopy, X-ray diffraction and scanning-electron microscopy. The microhardness distribution of the coatings after laser processing is also measured. The results reveal that Ni-based amorphous composite coatings have successfully been fabricated on mild steel substrate at low dilution ratio when the cladding power was 700 W, 800 W and 900 W. While at high laser power of 1000 W, no amorphous phase was found. The coatings with low dilution ratio exhibit the highest microhardness of 1200 HV0.5 due to their largest volume fraction of amorphous phase.
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NASA Astrophysics Data System (ADS)
Ohmori, H.; Shoji, M.; Kobayashi, T.; Yamamoto, T.; Sugiyama, Y.; Hayashi, K.; Hono, K.
1996-04-01
The Hf-added FeRuGaSi alloy film has an amorphous structure in the as-deposited state and becomes nanocrystalline after annealing. Due to this structure change from crystalline to amorphous by the addition of Hf, soft magnetic degradation of the film deposited on the slant grooved substrate, which is necessary for the sophisticated embedded thin film (ETF) head structure, is greatly suppressed and the undesirable film stress is relieved. The FeRuGaSi-Hf alloy film has higher resistivity and permeability at high frequencies than those of sendust film, and the read/write characteristics of this alloy film show better performance than sendust film.
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NASA Astrophysics Data System (ADS)
Kuzmann, E.; Stichleutner, S.; Doyle, O.; Chisholm, C. U.; El-Sharif, M.; Homonnay, Z.; Vértes, A.
2005-04-01
Constant current technique was applied to electrodeposit tin-containing coatings such as tin-cobalt (Sn-Co), tin-iron (Sn-Fe) and a novel tin-cobalt-iron (Sn-Co-Fe) from a gluconate bath. The effect of plating parameters (current density, deposition time at an electrolyte temperature of 60°C and pH=7.0) on phase composition, crystal structure and magnetic anisotropy of alloy deposits has been investigated mainly by 57Fe CEMS, 119Sn CEMS and transmission Mössbauer Spectroscopy as well as XRD. 57Fe and 119Sn CEM spectra and XRD reflect that the dominant phases of the deposits are orthorhombic Co3Sn2, tetragonal FeSn2 or amorphous Fe-Sn and amorphous Sn-Co-Fe in Sn-Co, Sn-Fe and Sn-Co-Fe coatings, respectively. Furthermore, the relative area of the 2nd and 5th lines of the sextets representing the magnetic iron containing phases decreases continuously with increasing current density in all Fe-containing deposits. At the same time, no essential change in the magnetic anisotropy can be found with the plating time. 119Sn spectra reveal the presence of small amount of β-Sn besides the main phases in Sn-Fe and in the Sn-Co coatings. Magnetically split 119Sn spectra reflecting transferred hyperfine field were observed in the case of Co-Sn-Fe coatings.
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Demonstration and Analysis of Materials Processing by Ablation Plasma Ion Implantation (APII)
NASA Astrophysics Data System (ADS)
Qi, B.; Gilgenbach, R. M.; Lau, Y. Y.; Jones, M. C.; Lian, J.; Wang, L. M.; Doll, G. L.; Lazarides, A.
2001-10-01
Experiments have demonstrated laser-ablated Fe ion implantation into Si substrates. Baseline laser deposited films (0 kV) showed an amorphous Fe-Si film overlying the Si substrate with a top layer of nanocrystalline Fe. APII films exhibited an additional Fe ion-induced damage layer, extending 7.6 nm below the Si surface. The overlying Fe-Si layer and Fe top layer were amorphized by fast ions. Results were confirmed by XPS vs Ar ion etching time for depth profile of the deposited films. XPS showed primarily Fe (top layer), transitioning to roughly equal Fe/Si , then mostly Si with lower Fe (implanted region). These data clearly prove Fe ion implantation into Si, verifying the feasibility of APII as an ion acceleration and implantation process [1]. SRIM simulations predict about 20 percent deeper Fe ion penetration than data, due to:(a) Subsequent ions must pass through the Fe film deposited by earlier ions, and (b) the bias voltage has a slow rise and fall time. Theoretical research has developed the scaling laws for APII [2]. Recently, a model has successfully explained the shortening of the decay time in the high voltage pulse with the laser ablation plasma. This reduces the theoretical RC time constant, which agrees with the experimental data. * Research supported by National Science Foundation Grant CTS-9907106 [1] Appl. Phys. Lett. 78, 3785 (2001) [2] Appl. Phys. Lett. 78, 706 (2001)),
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Fe and O EELS Studies of Ion Irradiated Murchison CM2 Carbonaceous Chondrite Matrix
NASA Technical Reports Server (NTRS)
Keller, L. P.; Christofferson, R.; Dukes, C. A.; Baragiola, R. A.; Rahman, Z.
2015-01-01
Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We also obtained O Ka spectra from phyllosilicates in both regions of the sample. The O Ka spectra show a pre-edge feature at approximately 530.5 electronvolts that is related to O 2p states hybridized with Fe 3d states. The intensity ratio of the O Ka pre-edge peak relative to the main part of the O Ka edge (that results from transitions of O 1s to 2p states) is lower in the irradiated layer compared to the pristine material and may reflect the loss of O (as OH) as was observed by IR spectroscopy. Conclusions: In addition to amorphization and OH loss, EELS spectra of He(+) irradiated matrix phyllosilicates in Murchison show that some of the Fe(3+) is reduced to Fe(2+). Spectral deconvolution is underway to extract quantitative ratios from the EELS spectra.
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Molybdenum isotope fractionation during complexation with organic matter in the Critical Zone
NASA Astrophysics Data System (ADS)
King, E. K.; Pett-Ridge, J. C.; Perakis, S. S.
2016-12-01
Molybdenum (Mo) is a micronutrient and a redox sensitive trace metal that also forms strong complexes with organic matter (OM). The fractionation of Mo in sediments associated with adsorption onto both iron (Fe) and manganese (Mn) (oxyhydr)oxides under oxic conditions and sulfide phases under euxinic conditions has been used to constrain redox conditions in the ocean. Additionally, Mo isotope dynamics in terrestrial systems can shed light on the pedogenic mechanisms driving the riverine Mo isotopic composition and how atmospheric inputs alter the trace metal budget and isotopic composition of soils. As a result of these studies, it has been hypothesized that multiple mechanisms are responsible for fractionating Mo isotopes. In particular, Mo fractionation during adsorption onto OM is unknown, despite the fact this mechanism is 3x to more than 20x greater than adsorption onto Fe- and Mn- (oxyhydr)oxides across a range of soil types from Oregon, Iceland, and Hawaii1-3 (Marks et al., 2015; Siebert et al., 2015; King et al., 2016). In this study, we measured Mo adsorption and isotopic fractionation onto insolubilized humic acid (IHA), a proxy for OM, as a function of both adsorption time (2-170 h) and pH (2-7). Preliminary results suggest that for the time series experiment, Mo adsorption onto IHA increased from 35% to 64% and a plateau was reached after 24 hours. The average Mo isotope fractionation between the solution and the IHA was Δ98Mosolution-IHA = 1.8 ± 0.3‰. For the pH series experiment, the average Mo isotope fractionation was Δ98Mosolution-IHA = 2.0 ± 0.2‰. Next, we compared the Mo isotopic composition of foliage, O-horizon, and surface soil from 12 sites in the Oregon Coast Range to better understand the impact of OM on Mo isotope dynamics in natural samples. The potential isotopic offset between dissolved and adsorbed Mo onto OM is of the same order of magnitude and direction as fractionation onto Fe- and Mn- (oxyhydr)oxides such as ferrihydrite, hematite, and birnessite which have Δ98Mosolution-oxide values of 1.1‰, 2.2‰, and 1.8‰, respectively (Goldberg et al., 2009; Wasylenki et al., 2011). These results have important implications for the interpretation of the sedimentary Mo record, its use as a paleoredox tracer, and its potential to record changes in the terrestrial weathering environment.
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Sklute, Elizabeth C.; Rogers, A. Deanne; Gregerson, Jason C.; Jensen, Heidi B.; Reeder, Richard J.; Dyar, M. Darby
2018-01-01
Salts with high hydration states have the potential to maintain high levels of relative humidity (RH) in the near subsurface of Mars, even at moderate temperatures. These conditions could promote deliquescence of lower hydrates of ferric sulfate, chlorides, and other salts. Previous work on deliquesced ferric sulfates has shown that when these materials undergo rapid dehydration, such as that which would occur upon exposure to present day Martian surface conditions, an amorphous phase forms. However, the fate of deliquesced halides or mixed ferric sulfate-bearing brines are presently unknown. Here we present results of rapid dehydration experiments on Ca–, Na–, Mg– and Fe–chloride brines and multi-component (Fe2 (SO4)3 ± Ca, Na, Mg, Fe, Cl, HCO3) brines at ∼21°C, and characterize the dehydration products using visible/near-infrared (VNIR) reflectance spectroscopy, mid-infrared attenuated total reflectance spectroscopy, and X-ray diffraction (XRD) analysis. We find that rapid dehydration of many multicomponent brines can form amorphous solids or solids with an amorphous component, and that the presence of other elements affects the persistence of the amorphous phase under RH fluctuations. Of the pure chloride brines, only Fe–chloride formed an amorphous solid. XRD patterns of the multicomponent amorphous salts show changes in position, shape, and magnitude of the characteristic diffuse scattering observed in all amorphous materials that could be used to help constrain the composition of the amorphous salt. Amorphous salts deliquesce at lower RH values compared to their crystalline counterparts, opening up the possibility of their role in potential deliquescence-related geologic phenomena such as recurring slope lineae (RSLs) or soil induration. This work suggests that a wide range of aqueous mixed salt solutions can lead to the formation of amorphous salts and are possible for Mars; detailed studies of the formation mechanisms, stability and transformation behaviors of amorphous salts are necessary to further constrain their contribution to Martian surface materials. PMID:29670302
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Surface modified mesostructured iron oxyhydroxide: synthesis, ecotoxicity, and application.
Choi, Jae-Woo; Mahendran, Basuvaraj; Chung, Seung-Gun; Kim, Song-Bae; Lee, Sang-Hyup
2014-12-01
Mesoporous iron oxide, particularly amine-functionalized FeO(x) and FeO(x), was investigated for the removal of toxic heavy metal anions of arsenic and chromium from an aqueous solution. As a control experiment for these toxic compounds, adsorption tests were also performed on Fe3O4 as their counterpart bulk chemical. The mesostructures were confirmed by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscopy (TEM). In addition, we prepared stock suspensions of meso-FeO(x), amine-functionalized meso-FeO(x) and Fe3O4 particles, and compared their acute toxicity against Daphnia magna. The 24 h-EC50 values of the amine-functionalized meso-FeO(x), meso-FeO(x) and Fe particle suspensions used in this study were 1682, 2549 and 95 mg/L, respectively. Organism toxicity caused by spills of adsorbents can be negated when the amine-functionalized meso-FeO(x), up to 1500 mg/L, is used as the adsorbent for heavy metal treatment. The adsorption of arsenic and chromium by the three adsorbents were examined, and different adsorption models were used to describe the equilibrium and kinetic data. The amine-functionalized meso-FeO(x) adsorbent was found to give the maximum adsorption capacities for arsenic and chromium (33.51 and 25.05 mg/g, respectively). This research gives promising results for the application of modified meso-FeO(x) as an adsorbent of toxic heavy metal anions from aqueous solutions.
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Kim, Cheolyong; Ahn, Jun-Young; Kim, Tae Yoo; Shin, Won Sik; Hwang, Inseong
2018-03-20
The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.
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Hosono, Eiji; Wang, Yonggang; Kida, Noriyuki; Enomoto, Masaya; Kojima, Norimichi; Okubo, Masashi; Matsuda, Hirofumi; Saito, Yoshiyasu; Kudo, Tetsuichi; Honma, Itaru; Zhou, Haoshen
2010-01-01
A triaxial LiFePO4 nanowire with a multi wall carbon nanotube (VGCF:Vapor-grown carbon fiber) core column and an outer shell of amorphous carbon was successfully synthesized through the electrospinning method. The carbon nanotube core oriented in the direction of the wire played an important role in the conduction of electrons during the charge-discharge process, whereas the outer amorphous carbon shell suppressed the oxidation of Fe2+. An electrode with uniformly dispersed carbon and active materials was easily fabricated via a single process by heating after the electrospinning method is applied. Mossbauer spectroscopy for the nanowire showed a broadening of the line width, indicating a disordered coordination environment of the Fe ion near the surface. The electrospinning method was proven to be suitable for the fabrication of a triaxial nanostructure.
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Synthesis and characterization of Fe(III)-silicate precipitation tubes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Parmar, K.; Pramanik, A.K.; Bandyopadhya, N.R.
2010-09-15
Fe(III)-silicate precipitation tubes synthesized through 'silica garden' route have been characterized using a number of analytical techniques including X-ray diffraction, infrared spectroscopy, atomic force microscopy, scanning and transmission electron microscopy. These tubes are brittle and amorphous and are hierarchically built from smaller tubes of 5-10 nm diameters. They remain amorphous at least up to 650 {sup o}C. Crystobalite and hematite are the major phases present in Fe(III)-silicate tubes heated at 850 {sup o}C. Morphology and chemical compositions at the external and internal walls of these tubes are remarkably different. These tubes are porous with high BET surface area of 291.2more » m{sup 2}/g. Fe(III)-silicate tubes contain significant amount of physically and chemically bound moisture. They show promise as an adsorbent for Pb(II), Zn(II), and Cr(III) in aqueous medium.« less
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NASA Astrophysics Data System (ADS)
Lee, Jung Gu; Lee, Gyoung-Ja; Park, Jin-Ju; Lee, Min-Ku
2017-05-01
The compositional effects of ternary Zr-Cu-X (X: Al, Fe) amorphous filler alloys on galvanic corrosion susceptibility in high-temperature pressurized water were investigated for Zircaloy-4 brazed joints. Through an Al-induced microgalvanic reaction that deteriorated the overall nobility of the joint, application of the Zr-Cu-Al filler alloy caused galvanic coupling to develop readily between the Al-bearing joint and the Al-free base metal, finally leading to massive localized corrosion of the joint. Contrastingly, joints prepared with a Zr-Cu-Fe filler alloy showed excellent corrosion resistance comparable to that of the Zircaloy-4 base metal, since the Cu and Fe elements forming fine intermetallic particles with Zr did not influence the electrochemical stability of the resultant joints. The present results demonstrate that Fe is a more suitable alloying element than Al for brazing filler alloys subjected to high-temperature corrosive environments.
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Thorat, Alpana A; Forny, Laurent; Meunier, Vincent; Taylor, Lynne S; Mauer, Lisa J
2017-12-27
The effects of salts on the stability of amorphous sucrose and its crystallization in different environments were investigated. Chloride (LiCl, NaCl, KCl, MgCl 2 , CaCl 2 , CuCl 2 , FeCl 2 , FeCl 3 , and AlCl 3 ) and sulfate salts with the same cations (Na 2 SO 4 , K 2 SO 4 , MgSO 4 , CuSO 4 , Fe(II)SO 4 , and Fe(III)SO 4 ) were studied. Samples (sucrose controls and sucrose:salt 1:0.1 molar ratios) were lyophilized, stored in controlled temperature and relative humidity (RH) conditions, and monitored for one month using X-ray diffraction. Samples were also analyzed by differential scanning calorimetry, microscopy, and moisture sorption techniques. All lyophiles were initially amorphous, but during storage the presence of a salt had a variable impact on sucrose crystallization. While all samples remained amorphous when stored at 11 and 23% RH at 25 °C, increasing the RH to 33 and 40% RH resulted in variations in crystallization onset times. The recrystallization time generally followed the order monovalent cations < sucrose < divalent cations < trivalent cations. The presence of a salt typically increased water sorption as compared to sucrose alone when stored at the same RH; however, anticrystallization effects were observed for sucrose combined with salts containing di- and trivalent cations in spite of the increased water content. The cation valency and hydration number played a major role in dictating the impact of the added salt on sucrose crystallization.
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Sokolowski, A; Wolowicz, M; Hummel, H
2001-10-01
Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.
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Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?
NASA Astrophysics Data System (ADS)
Nuester, J.; Liermann, L. J.; Brantley, S. L.
2006-12-01
Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in significant iron isotope effects, and we are testing for these effects. For example, we expect to see enrichment of light isotopes in the early released fractions as iron is reduced (like effects observed by Wiederhold et al. (2006) for ligand-controlled and reductive dissolution of goethite). Such kinetic isotope effects should be particularly strong for iron release from siderophores with high Fe affinities like DFMB (log ß_(Fe(III)) = 30.60). We are also investigating other mechanisms to liberate iron from organic ligands including a pathway with extracellular iron reductases.
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NASA Astrophysics Data System (ADS)
Kane, S. N.; Shah, M.; Satalkar, M.; Gehlot, K.; Kulriya, P. K.; Avasthi, D. K.; Sinha, A. K.; Modak, S. S.; Ghodke, N. L.; Reddy, V. R.; Varga, L. K.
2016-07-01
Effect of 80 MeV 16O6+ ion irradiation in amorphous Fe77P8Si3C5Al2Ga1B4 alloy is reported. Electronic energy loss induced modifications in the structural and, magnetic properties were monitored by synchrotron X-ray diffraction (SXRD), Mössbauer and, magnetic measurements. Broad amorphous hump seen in SXRD patterns reveals the amorphous nature of the studied specimens. Mössbauer measurements suggest that: (a) alignment of atomic spins within ribbon plane, (b) changes in average hyperfine field suggests radiation-induced decrease in the inter atomic distance around Mössbauer (Fe) atom, (c) hyperfine field distribution confirms the presence of non-magnetic elements (e.g. - B, P, C) in the first near-neighbor shell of the Fe atom, thus reducing its magnetic moment, and (d) changes in isomer shift suggests variation in average number of the metalloid near neighbors and their distances. Minor changes in soft magnetic behavior - watt loss and, coercivity after an irradiation dose of 2 × 1013 ions/cm2 suggests prospective application of Fe77P8Si3C5Al2Ga1B4 alloy as core material in accelerators (radio frequency cavities).
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Transmission electron microscope analyses of alteration phases in martian meteorite MIL 090032
NASA Astrophysics Data System (ADS)
Hallis, L. J.; Ishii, H. A.; Bradley, J. P.; Taylor, G. J.
2014-06-01
The nakhlite group of martian meteorites found in the Antarctic contain varying abundances of both martian and terrestrial secondary alteration phases. The aim of this study was to use transmission electron microscopy (TEM) to compare martian and terrestrial alteration embodied within a single nakhlite martian meteorite find - MIL 090032. Martian alteration veins in MIL 090032 are composed of poorly ordered Fe-smectite phyllosilicate. This poorly-ordered smectite appears to be equivalent to the nanocrystalline phyllosilicate/hydrated amorphous gel phase previously described in the martian alteration veins of other nakhlites. Chemical differences in this nanocrystalline phyllosilicate between different nakhlites imply localised alteration, which occurred close to the martian surface in MIL 090032. Both structurally and compositionally the nakhlite nanocrystalline phyllosilicate shows similarities to the amorphous/poorly ordered phase recently discovered in martian soil by the Mars Curiosity Rover at Rocknest, Gale Crater. Terrestrially derived alteration phases in MIL 090032 include jarosite and gypsum, amorphous silicates, and Fe-oxides and hydroxides. Similarities between the mineralogy and chemistry of the MIL 090032 terrestrial and martian alteration phases suggest the alteration conditions on Mars were similar to those in the Antarctic. At both sites a small amount of fluid at low temperatures infiltrated the rock and became acidic as a result of the conversion of Fe2+ to Fe3+ under oxidising conditions.
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NASA Astrophysics Data System (ADS)
Limbu, Dil; Biswas, Parthapratim
We present a simple and efficient Monte-Carlo (MC) simulation of Iron (Fe) and Nickel (Ni) clusters with N =5-100 and amorphous Silicon (a-Si) starting from a random configuration. Using Sutton-Chen and Finnis-Sinclair potentials for Ni (in fcc lattice) and Fe (in bcc lattice), and Stillinger-Weber potential for a-Si, respectively, the total energy of the system is optimized by employing MC moves that include both the stochastic nature of MC simulations and the gradient of the potential function. For both iron and nickel clusters, the energy of the configurations is found to be very close to the values listed in the Cambridge Cluster Database, whereas the maximum force on each cluster is found to be much lower than the corresponding value obtained from the optimized structural configurations reported in the database. An extension of the method to model the amorphous state of Si is presented and the results are compared with experimental data and those obtained from other simulation methods. The work is partially supported by the NSF under Grant Number DMR 1507166.
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NASA Astrophysics Data System (ADS)
Romanov, I. Yu.; Gushchina, N. V.; Ovchinnikov, V. V.; Makhinko, F. F.; Stepanov, A. V.; Medvedev, A. I.; Starodubtsev, Yu. N.; Belozerov, V. Ya.; Loginov, B. A.
2018-02-01
Using the methods of X-ray diffraction and atomic force microscopy, the process of crystallization of an amorphous Fe72.5Cu1Nb2Mo1.5Si14B9 alloy irradiated with accelerated Ar+ ions is investigated. It is found out that an irradiation by the Ar+ ions with the energy 30 keV at the ion current density 300 μA/cm2 (fluence 3.75·1015 cm-2, irradiation time 2 s, ion-beam short-duration heating up to 350°C, which is 150°C lower than the thermal crystallization threshold) results in a complete crystallization of this amorphous alloy (throughout the bulk of a 25 μm ribbon) followed by precipitation of solid solution crystals of α-Fe(Si), close in its composition to Fe80Si20, stable phase of Fe3Si, and metastable hexagonal phases. By the methods of atomic force and scanning tunneling microscopy it is shown that nanocrystallization caused by ion irradiation is accompanied by surface relief changes both on the irradiated and unirradiated sides of the Fe72.5Cu1Nb2Mo1.5Si14B9 alloy ribbon at the depth exceeding by a factor of 103 that of the physical ion penetration for this material. The data obtained, taking into account a significant temperature decrease and multiple acceleration of the crystallization process, serve an evidence of the radiation-dynamic influence of accelerated ions on the metastable amorphous medium.
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NASA Astrophysics Data System (ADS)
Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.
2006-03-01
Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.
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Shopska, M; Paneva, D; Kadinov, G; Cherkezova-Zheleva, Z; Mitov, I; Iliev, M
2017-03-01
The biogenic iron oxide/hydroxide materials possess useful combination of physicochemical properties and are considered for application in various areas. Their production does not require special investments because these compounds are formed during cultivation of neurophilic iron bacteria. Bacteria from genus Leptothrix develop intensively in the Sphaerotilus-Leptothrix group of bacteria isolation medium and feeding media of Fedorov and Lieske. These media are different in their composition which determined the present study as an attempt to clear up the reasons that define the differences in the composition of the laboratory-obtained biomasses and the natural biomass finds. FTIRS, Mössbauer spectroscopy, and XRD were used in the research. Comparative analysis showed that the biomass and control samples contain iron compounds (α-FeOOH, γ-FeOOH, β-FeOOH, γ-Fe 2 O 3 ) in different ratios. The biomass samples were enriched in oxyhydroxides of higher dispersion. Organic residuals of bacterial origin, SO 4 , CO 3 , and PO 4 groups were registered in the biogenic materials.
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Study on preparation of ultrafine amorphous particles by chemical reduction
NASA Astrophysics Data System (ADS)
Song, Xu; Yusheng, Xu; Huali, Jiang; Qing, Xue
1993-04-01
Ultrafine amorphous FeNiB powder was prepared by potassium borohydride reduction by mixing the aqueous solutions in a bath of supersonic oscillator. Different mixing ratios of potassium borohydride to metal salt were applied. Analysis of the composition of the sample and the Fe 2+ and Ni 2+ remaining in the filtrate after preparation shows that a quantity of KBH 4 about 1.5 times the stoichiometrical quantity is enough. Mössbauer measurements were performed at room temperature and it was found that excess KBH 4 makes no distinct difference in the spectra of the samples.
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Brazing Inconel 625 Using Two Ni/(Fe)-Based Amorphous Filler Foils
NASA Astrophysics Data System (ADS)
Chen, Wen-Shiang; Shiue, Ren-Kae
2012-07-01
For MBF-51 filler, the brazed joint consists of interfacial grain boundary borides, coarse Nb6Ni16Si7, and Ni/Cr-rich matrix. In contrast, the VZ-2106 brazed joint is composed of interfacial Nb6Ni16Si7 precipitates as well as grain boundary borides, coarse Nb6Ni16Si7, and Ni/Cr/Fe-rich matrix. The maximum tensile strength of 443 MPa is obtained from the MBF-51 brazed specimen. The tensile strengths of VZ-2106 brazed joints are approximately 300 MPa. Both amorphous filler foils demonstrate potential in brazing IN-625 substrate.
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Tuning the Magnetic and Electronic Properties of Iron(x )Silicon(1-x) Thin Films for Spintronics
NASA Astrophysics Data System (ADS)
Karel, Julie Elizabeth
This dissertation investigated the magnetic and electronic properties of a potentially better alternative: off-stoichimetry, bcc-like FexSi 1-x thin films (0.43
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Thermal effect on structural and magnetic properties of Fe78B13Si9 annealed amorphous ribbons
NASA Astrophysics Data System (ADS)
Soltani, Mohamed Larbi; Touares, Abdelhay; Aboki, Tiburce A. M.; Gasser, Jean-Georges
2017-08-01
In the present work, we study the influence of thermal treatments on the magnetic properties of as-quenched and pre-crystallized Fe78Si9B13 after stress relaxation. The crystallization behavior of amorphous and treated Fe78Si9B13 ribbons was revisited. The measurements were carried out by means of Differential Scanning Calorimetry, by X-ray diffraction and by Vibrating Sample Magnetometer, Susceptometer and fluxmeter. Relaxed samples were heated in the resistivity device up to 700°C and annealed near the onset temperature about 420°C for respectively 1, 3, 5, 8 hours. In as-quenched samples, two transition points occur at about 505°C and 564°C but in relaxed sample, the transition points have been found about 552°C and 568°C. Kinetics of crystallization was deduced for all studied samples. Annealing of the as-purchased ribbon shows the occurrence of α-Fe and tetragonal Fe3B resulting from the crystallization of the remaining amorphous phase. The effects on magnetic properties were pointed out by relating the structural evolution of the samples. The magnetic measurements show that annealing change the saturation magnetization and the coercive magnetic field values, hence destroying the good magnetic properties of the material. The heat treatment shows that the crystallization has greatly altered the shape of the cycles and moved the magnetic saturation point of the samples. The effect of treatment on the magneto-crystalline anisotropy is also demonstrated.
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NASA Astrophysics Data System (ADS)
Chang, Liang; Xie, Lei; Liu, Min; Li, Qiang; Dong, Yaqiang; Chang, Chuntao; Wang, Xin-Min; Inoue, Akihisa
2018-04-01
FeSiBPNbCu nanocrystalline powder cores (NPCs) with excellent magnetic properties were fabricated by cold-compaction of the gas-atomized amorphous powder. Upon annealing at the optimum temperature, the NPCs showed excellent magnetic properties, including high initial permeability of 88, high frequency stability up to 1 MHz with a constant value of 85, low core loss of 265 mW/cm3 at 100 kHz for Bm = 0.05 T, and superior DC-bias permeability of 60% at a bias field of 100 Oe. The excellent magnetic properties of the present NPCs could be attributed to the ultrafine α-Fe(Si) phase precipitated in the amorphous matrix and the use of gas-atomized powder coated with a uniform insulation layer.
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NASA Astrophysics Data System (ADS)
Opfergelt, S.; Williams, H. M.; Cornelis, J. T.; Guicharnaud, R. A.; Georg, R. B.; Siebert, C.; Gislason, S. R.; Halliday, A. N.; Burton, K. W.
2017-11-01
Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (Δ57Fesolution-soil = -0.11 ± 0.12‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (Δ57Fesolution-soil = -0.41 ± 0.32‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (Δ30Sisolution-soil = 0.92 ± 0.26‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (Δ30Sisolution-soil = 1.63 ± 0.40‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal-organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal-organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with warming high latitude peatlands, Fe export from soils as Fe-organic complexes will increase, which in turn has implications for Fe transport in rivers, and ultimately the delivery of Fe to the oceans.
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Mode of occurrence of arsenic in feed coal and its derivative fly ash, Black Warrior Basin, Alabama
Zielinski, R.A.; Foster, A.L.; Meeker, G.P.; Brownfield, I.K.
2007-01-01
An arsenic-rich (As = 55 ppm) bituminous feed coal from the Black Warrior Basin, Alabama and its derivative fly ash (As = 230 ppm) were selected for detailed investigation of arsenic residence and chemical forms. Analytical techniques included microbeam analysis, selective extraction, and As K-edge X-ray absorption fine-structure (XAFS) spectroscopy. Most As in the coal is contained in a generation of As-bearing pyrite (FeS2) that formed in response to epigenetic introduction of hydrothermal fluids. XAFS results indicate that approximately 50% of the As in the coal sample occurs as the oxidized As(V) species, possibly the result of incipient oxidation of coal and pyrite prior to our analysis. Combustion of pyrite and host coal produced fly ash in which 95% of As is present as As(V). Selective extraction of the fly ash with a carbonate buffer solution (pH = 10) removed 49% of the As. A different extraction with an HCl-NH2OH mixture, which targets amorphous and poorly crystalline iron oxides, dissolved 79% of the As. XAFS spectroscopy of this highly acidic (pH = 3.0) fly ash indicated that As is associated with some combination of iron oxide, oxyhydroxide, or sulfate. In contrast, a highly alkaline (pH = 12.7) fly ash from Turkey shows most As associated with a phase similar to calcium orthoarsenate (Ca3(AsO4)2). The combined XAFS results indicate that fly ash acidity, which is determined by coal composition and combustion conditions, may serve to predict arsenic speciation in fly ash.
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Barco, Roman A; Emerson, David; Sylvan, Jason B; Orcutt, Beth N; Jacobson Meyers, Myrna E; Ramírez, Gustavo A; Zhong, John D; Edwards, Katrina J
2015-09-01
Microaerophilic, neutrophilic, iron-oxidizing bacteria (FeOB) grow via the oxidation of reduced Fe(II) at or near neutral pH, in the presence of oxygen, making them relevant in numerous environments with elevated Fe(II) concentrations. However, the biochemical mechanisms for Fe(II) oxidation by these neutrophilic FeOB are unknown, and genetic markers for this process are unavailable. In the ocean, microaerophilic microorganisms in the genus Mariprofundus of the class Zetaproteobacteria are the only organisms known to chemolithoautotrophically oxidize Fe and concurrently biomineralize it in the form of twisted stalks of iron oxyhydroxides. The aim of this study was to identify highly expressed proteins associated with the electron transport chain of microaerophilic, neutrophilic FeOB. To this end, Mariprofundus ferrooxydans PV-1 was cultivated, and its proteins were extracted, assayed for redox activity, and analyzed via liquid chromatography-tandem mass spectrometry for identification of peptides. The results indicate that a cytochrome c4, cbb3-type cytochrome oxidase subunits, and an outer membrane cytochrome c were among the most highly expressed proteins and suggest an involvement in the process of aerobic, neutrophilic bacterial Fe oxidation. Proteins associated with alternative complex III, phosphate transport, carbon fixation, and biofilm formation were abundant, consistent with the lifestyle of Mariprofundus. Copyright © 2015, American Society for Microbiology. All Rights Reserved.
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Mössbauer Study and Modeling of Iron Import and Trafficking in Human Jurkat Cells
Jhurry, Nema D.; Chakrabarti, Mrinmoy; McCormick, Sean P.; Gohil, Vishal M.; Lindahl, Paul A.
2014-01-01
The Fe content of Jurkat cells grown on transferrin-bound iron (TBI) and FeIII citrate (FC) was characterized using Mössbauer, EPR, and UV-vis spectroscopies, electron microscopy, and ICP-MS. Isolated mitochondria were similarly characterized. Fe-limited cells contained ∼ 100 μM of essential Fe, mainly as mitochondrial Fe and non-mitochondrial nonheme high-spin (NHHS) FeII. Fe-replete cells also contained ferritin-bound Fe and FeIII oxyhydroxide nanoparticles. Only 400 ± 100 Fe ions were loaded per ferritin complex, regardless of the growth medium Fe concentration. Ferritin regulation thus appears more complex than is commonly assumed. The magnetic/structural properties of Jurkat nanoparticles differed from those in yeast mitochondria. They were smaller and may be located in the cytosol. The extent of nanoparticle formation scaled nonlinearly with the concentration of Fe in the medium. Nanoparticle formation was not strongly correlated with ROS damage. Cells could utilize nanoparticle Fe, converting such aggregates into essential Fe forms. Cells grown on galactose rather than glucose respired faster, grew slower, exhibited more ROS damage and generally contained more nanoparticles. Cells grown with TBI rather than FC contained lower Fe concentrations, more ferritin and fewer nanoparticles. Cells in which transferrin receptor expression was increased contained more ferritin Fe. Frataxin-deficient cells contained more nanoparticles than comparable WT cells. Data were analyzed by a chemically-based mathematical model. Although simple, it captured essential features of Fe import, trafficking and regulation. TBI import was highly regulated but FC import was not. Nanoparticle formation was not regulated but the rate was third-order in cytosolic Fe. PMID:24180611
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Coeval Formation of Aqueous Minerals on Mars
NASA Astrophysics Data System (ADS)
Fairen, A.; Uceda, E.; Gil, C.; Palmero Rodriguez, A.; Gago-Duport, L.
2015-12-01
Understanding the geochemical conditions on early Mars requires an explanation for the presence of sulfates and phyllosilicates, which must be also consistent with the absence of widespread sedimentary carbonates. In addition, sulfates and phyllosilicates do not generally occur together on Mars, which has been interpreted as a marker for detached mineral formation due to differing planetary environmental conditions separated dramatically, either in time or in space. Here, thermodynamic equilibrium calculations are used to determine the stability boundaries for phyllosilicates, ferrous and ferric sulfates, carbonates and iron oxyhydroxides precipitation on early Mars, at different atmospheric CO2 pressures and both under reducing and oxidizing conditions. Results suggest that phyllosilicates formed in mildly acidic to alkaline aqueous solutions, with a pH>4 for nontronite and a pH>6 for other smectites with low content in Fe and Mg (montmorillonite, saponite). Sulfate deposition dominates in solutions moderately to highly acidic, with a pH<6 conducive to the synthesis of kieserite. In the overlapping phyllosilicates/sulfates pH range, between 4 and 6, a competition for Mg between nontronite and kieserite is expected, and the formation of nontronite would be favored in areas where SiO2 activity in surface waters was high as a result of intense weathering of the early basaltic crust. Carbonates formed at pH>6, overlapping with the synthesis of low-Fe-Mg smectites. Model calculations anticipate the co-precipitation of smectites and siderite or any alteration product that could have resulted from the later substitution of Fe in siderite, such as Mg- or Mn-carbonate, triggering a competition for Mg between magnesite and low-Fe-Mg smectites. As expected, the model does not predict coeval synthesis of carbonates and sulfates. Goethite and other oxyhydroxides precipitate at pH below 2, a range at which jarosite and goethite are the expected iron-bearing phases. These results suggest that the major water-alteration products on the Martian surface were deposited simultaneously in space and in time, creating diverse geochemical conditions over the entire surface of a cold Mars during the wet Noachian/Hesperian times.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Zarzycki, Piotr; Rosso, Kevin M.
Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), wemore » developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.« less
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NASA Technical Reports Server (NTRS)
Sutter, B.; Wasowicz, T.; Howard, T.; Hossner, L. R.; Ming, D. W.
2002-01-01
The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.
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Sulfide mineralization: Its role in chemical weathering of Mars
NASA Technical Reports Server (NTRS)
Burns, Roger G.
1988-01-01
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.
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Weathering of sulfides on Mars
NASA Technical Reports Server (NTRS)
Burns, Roger G.; Fisher, Duncan S.
1987-01-01
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.
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Schwertmannite stability in acidified coastal environments
NASA Astrophysics Data System (ADS)
Collins, Richard N.; Jones, Adele M.; Waite, T. David
2010-01-01
A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.
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Trace metals in the Ob and Yenisei Rivers' Estuaries (the Kara Sea).
NASA Astrophysics Data System (ADS)
Demina, L. L.
2014-12-01
Behavior of some trace metals (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb) in water column (soluble <0.45 µm and particulate fractions) and bottom sediments (surface and cores) along the two transects from the Ob River and Yenisei River Estuaries to the Kara Sea was studied. The length of both transects was about 700 km. Water depth was 12-63 m, O2 dissolved :5.36-9.55 ml l-1. Along the transects salinity increased from 0.07 to 34.2 psu, while the SPM' concentration decreased from 10.31 to 0.31 mg/l. Total suspended particulate matter load is more than one order of magnitude higher in the Ob River Estuary comparing to that of the Yenisei River. It has led to a significant difference between the suspended trace metals' concentrations (µg/l) in water of the two estuaries. With salinity increase along transects Fe susp., Mn susp. and Zn susp. decreased by a factor of 100-500, that has led to a growth of a relative portion of dissolved trace metals followed by their bioaccumulation (Demina et al., 2010). A strong direct correlation between suspended Cu, Fe and SPM mass concentration was found. For the first time along the Yenisei River' Estuary -the Kara Sea transect a direct positive correlation between Cu suspended and volume concentration of SPM (mg/ml3) was found, that was attributed to contribution of phytoplankton aggregates in the SPM composition. A trend of relationship between content of suspended As and pelitic fraction (2-10 µm) of SPM was firstly found in theses basins also. Study of trace metal speciation in the bottom sediments (adsorbed, associated with Fe-Mn (oxyhydr)oxides, organic matter and fixed in the mineral lattice or refractory) has revealed the refractory fraction to be prevailing (70-95% total content) for Fe, Zn, Cu, Co, Ni, Cr, Cd and Pb. That means that toxic heavy metals were not available for bottom fauna. Mn was predominantly found in the adsorbed and (oxyhydr)oxides geochemically labile forms, reflecting the redox condition change along both transects and within the sedimentary cores. References. Demina L.L., Gordeev V.V., Galkin S.V., Kravchishina M.D. Biogeochemistry of some heavy metals and metalloids along the transect the Ob River Estuary - the Kara Sea. Oceanology, 2010, vo. 50, No 5, pp. 729- 742.
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Chemical processes for the extreme enrichment of tellurium into marine ferromanganese oxides
NASA Astrophysics Data System (ADS)
Kashiwabara, Teruhiko; Oishi, Yasuko; Sakaguchi, Aya; Sugiyama, Toshiki; Usui, Akira; Takahashi, Yoshio
2014-04-01
Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation. This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as in the case of some cations. This enrichment mechanism also means that ferromanganese oxides mainly scavenge dominant Te(VI) species from seawater and do not affect its species distribution in seawater, as described in a previous model. The variation in Te abundances and the correlation of Te concentration with the growth rate of natural ferromanganese oxides are consistent with the coprecipitation mechanism.
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Bauers, Sage R; Wood, Suzannah R; Jensen, Kirsten M Ø; Blichfeld, Anders B; Iversen, Bo B; Billinge, Simon J L; Johnson, David C
2015-08-05
Homogeneous reaction precursors may be used to form several solid-state compounds inaccessible by traditional synthetic routes, but there has been little development of techniques that allow for a priori prediction of what may crystallize in a given material system. Here, the local structures of FeSbx designed precursors are determined and compared with the structural motifs of their crystalline products. X-ray total scattering and atomic pair distribution function (PDF) analysis are used to show that precursors that first nucleate a metastable FeSb3 compound share similar local structure to the product. Interestingly, precursors that directly crystallize to thermodynamically stable FeSb2 products also contain local structural motifs of the metastable phase, despite their compositional disagreement. While both crystalline phases consist of distorted FeSb6 octahedra with Sb shared between either two or three octahedra as required for stoichiometry, a corner-sharing arrangement indicative of AX3-type structures is the only motif apparent in the PDF of either precursor. Prior speculation was that local composition controlled which compounds nucleate from amorphous intermediates, with different compositions favoring different local arrangements and hence different products. This data suggests that local environments in these amorphous intermediates may not be very sensitive to overall composition. This can provide insight into potential metastable phases which may form in a material system, even with a precursor that does not crystallize to the kinetically stabilized product. Determination of local structure in homogeneous amorphous reaction intermediates from techniques such as PDF can be a valuable asset in the development of systematic methods to prepare targeted solid-state compounds from designed precursors.
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Consani, Sirio; Carbone, Cristina; Dinelli, Enrico; Balić-Žunić, Tonci; Cutroneo, Laura; Capello, Marco; Salviulo, Gabriella; Lucchetti, Gabriella
2017-06-01
Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.
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Acid-Sulfate-Weathering Activity in Shergottite Sites on Mars Recorded in Grim Glasses
NASA Technical Reports Server (NTRS)
Rao, M. N.; Nyquist, L. E.; Ross, K.; Sutton, S. R.; Schwandt, C. S.
2011-01-01
Based on mass spectrometric studies of sulfur species in Shergotty and EET79001, [1] and [2] showed that sulfates and sulfides occur in different proportions in shergottites. Sulfur speciation studies in gas-rich impact-melt (GRIM) glasses in EET79001 by the XANES method [3] showed that S K-XANES spectra in GRIM glasses from Lith A indicate that S is associated with Ca and Al presumably as sulfides/sulfates whereas the XANES spectra of amorphous sulfide globules in GRIM glasses from Lith B indicate that S is associated with Fe as FeS. In these amorphous iron sulfide globules, [4] found no Ni using FE-SEM and suggested that the globules resulting from immiscible sulfide melt may not be related to the igneous iron sulfides having approximately 1-3% Ni. Furthermore, in the amorphous iron sulfides from 507 GRIM glass, [5] determined delta(sup 34)S values ranging from +3.5%o to -3.1%o using Nano-SIMS. These values plot between the delta(sup 34)S value of +5.25%o determined in the sulfate fraction in Shergotty [6] at one extreme and the value of -1.7%o obtained for igneous sulfides in EET79001 and Shergotty [7] at the other. These results suggest that the amorphous Fe-S globules likely originated by shock reduction of secondary iron sulfate phases occurring in the regolith precursor materials during impact [7]. Sulfates in the regolith materials near the basaltic shergottite sites on Mars owe their origin to surficial acid-sulfate interactions. We examine the nature of these reactions by studying the composition of the end products in altered regolith materials. For the parent material composition, we use that of the host shergottite material in which the impact glasses are situated.
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Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei
2016-05-01
Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments.
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Magnetic Properties of Amorphous Fe-Si-B Powder Cores Mixed with Pure Iron Powder
NASA Astrophysics Data System (ADS)
Kim, Hyeon-Jun; Nam, Seul Ki; Kim, Kyu-Sung; Yoon, Sung Chun; Sohn, Keun-Yong; Kim, Mi-Rae; Sul Song, Yong; Park, Won-Wook
2012-10-01
Amorphous Fe-Si-B alloy was prepared by melt-spinning, and then the ribbons were pulverized and ball-milled to make the amorphous powder of ˜25 µm in size. Subsequently those were mixed with pure iron powders with an average particle size of 3 µm, and 1.5 wt % water glass diluted by distilled water at the ratio of 1:2. The powder mixtures were cold compacted at 650 MPa in toroid die, and heat treated at 430-440 °C under a nitrogen atmosphere for 1 h and 30 min, respectively. The soft magnetic properties of powder core were investigated using a B-H analyzer and a flux meter at the frequency range of ˜100 kHz. The microstructure was observed using scanning electron microscope (SEM), and the density of the core was measured using the principle of Archimedes. Based on the experimental results, the amorphous powder mixed with pure iron powder showed the improved powder compactability, which resulted in the increased permeability and the reduced core loss.
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NASA Technical Reports Server (NTRS)
Morris, R. V.; Ming, D. W.; Gellert, R.; Vaniman, D. T.; Bish, D. L.; Blake, D. F.; Chipera, S. J.; Morrison, S. M.; Downs, R. T.; Rampe, E. B.;
2015-01-01
We have previously calculated the chemical compositions of the X-ray-diffraction (XRD) amorphous component of three solid samples (Rocknest (RN) soil, John Klein (JK) drill fines, and Cumberland (CB) drill fines) using major-element chemistry (APXS), volatile-element chemistry (SAM), and crystalline- phase mineralogy (CheMin) obtained by the Curiosity rover as a part of the ongoing Mars Science Laboratory mission in Gale Crater. According to CheMin analysis, the RN and the JK and CB samples are mineralogically distinct in that RN has no detectable clay minerals and both JK and CB have significant concentrations of high-Fe saponite. The chemical composition of the XRD amorphous component is the composition remaining after mathematical removal of the compositions of crystalline components, including phyllosilicates if present. Subsequent to, we have improved the unit cell parameters for Fe-forsterite, augite, and pigeonite, resulting in revised chemical compositions for the XRD-derived crystalline component (excluding clay minerals). We update here the calculated compositions of amorphous components using these revised mineral compositions.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mukhgalin, V. V.; Lad’yanov, V. I.
2015-08-17
The influence of the melt heat treatment on the structure and crystallization process of the rapidly quenched amorphous Fe{sub 78}B{sub 12}Si{sub 9}Ni{sub 1} alloys have been investigated by means of x-ray diffraction, DSC and TEM. Amorphous phase separation has been observed in the alloys quenched after the preliminary high temperature heat treatment of the liquid alloy (heating above 1400°C). Comparative analysis of the pair distribution functions demonstrates that this phase separation accompanied by a changes in the local atomic arrangement. It has been found that crystallization process at heating is strongly dependent on the initial amorphous phase structure - homogeneousmore » or phase separated. In the last case crystallization goes through the formation of a new metastable hexagonal phase [a=12.2849(9) Ǻ, c=7.6657(8) Ǻ]. At the same time the activation energy for crystallization (Ea) reduces from 555 to 475 kJ mole{sup −1}.« less
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Zeng, Xiang; Zhang, Zhao; Li, Xi; Zhang, Xiaobo; Cao, Junwei; Jebbar, Mohamed; Alain, Karine; Shao, Zongze
2015-02-01
A novel piezophilic, thermophilic, anaerobic, fermentative bacterial strain, designated strain DY22613(T), was isolated from a deep-sea hydrothermal sulfide deposit at the East Pacific Rise (GPS position: 102.6° W 3.1° S). Cells of strain DY22613(T) were long, motile rods (10 to 20 µm in length and 0.5 µm in width) with peritrichous flagella and were Gram-stain-negative. Growth was recorded at 44-72 °C (optimum 60-62 °C) and at hydrostatic pressures of 0.1-55 MPa (optimum 20 MPa). The pH range for growth was from pH 5.0 to 9.0 with an optimum at pH 7.0. Growth was observed in the presence of 1 to 8 % (w/v) sea salts and 0.65 to 5.2 % (w/v) NaCl, with optimum salt concentrations at 3.5 % for sea salts and at 2.3 % for NaCl. Under optimal growth conditions, the shortest generation time observed was 27 min (60 °C, 20 MPa). Strain DY22613(T) was heterotrophic, able to utilize complex organic compounds, amino acids, sugars and organic acids including peptone, tryptone, beef extract, yeast extract, alanine, glutamine, methionine, phenylalanine, serine, threonine, fructose, fucose, galactose, gentiobiose, glucose, mannose, melibiose, palatinose, rhamnose, turanose, pyruvate, lactic acid, methyl ester, erythritol, galacturonic acid and glucosaminic acid. Strain DY22613(T) was able to reduce Fe(III) compounds, including Fe(III) oxyhydroxide (pH 7.0), amorphous iron(III) oxide (pH 9.0), goethite (α-FeOOH, pH 12.0), Fe(III) citrate and elementary sulfur. Products of fermentation were butyrate, acetate and hydrogen. Main cellular fatty acids were iso-C15 : 0, iso-C14 : 0 3-OH and C14 : 0. The genomic DNA G+C content of strain DY22613(T) was 36.7 mol%. Based on 16S rRNA gene sequence analysis, the strain forms a novel lineage within the class Clostridia and clusters with the order Haloanaerobiales (86.92 % 16S rRNA gene sequence similarity). The phylogenetic data suggest that the lineage represents at least a novel genus and species, for which the name Anoxybacter fermentans gen. nov., sp. nov. is proposed. The type strain is DY22613(T) ( = JCM 19466(T) = DSM 28033(T) = MCCC 1A06456(T)). © 2015 IUMS.
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Impact of Ion Bombardment on the Structure and Magnetic Properties of Fe78Si13B9 Amorphous Alloy
NASA Astrophysics Data System (ADS)
Wu, Yingwei; Peng, Kun
2018-06-01
Amorphous Fe78Si13B9 alloy ribbons were bombarded by ion beams with different incident angles ( θ ). The evolution of the microstructure and magnetic properties of ribbons caused by ion beam bombardment was investigated by x-ray diffraction, transmission electron microscope and vibrating sample magnetometer analysis. Low-incident-angle bombardment led to atomic migration in the short range, and high-incident-angle bombardment resulted in the crystallization of amorphous alloys. Ion bombardment induces magnetic anisotropy and affects magnetic properties. The effective magnetic anisotropy was determined by applying the law of approach to saturation, and it increased with the increase of the ion bombardment angle. The introduction of effective magnetic anisotropy will reduce the permeability and increase the relaxation frequency. Excellent high-frequency magnetic properties can be obtained by selecting suitable ion bombardment parameters.
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Magnetic and thermal properties of amorphous TbFeCo alloy films
NASA Astrophysics Data System (ADS)
Wang, Ke; Dong, Shuo; Huang, Ya; Qiu, Yuzhen
2017-07-01
Amorphous TbFeCo material with perpendicular magnetic anisotropy is currently attracting more attention for potential applications in spintronic devices and logic memories. We systematically investigate magnetic, structural, thermal, optical and electrical properties of TbFeCo alloy films. It shows out-of-plane easy axis of the films turns into in-plane orientation after annealing. Significant increase in saturation magnetization in the temperature range between 400 and 450 °C is revealed by thermomagnetic measurements. The occurrence of crystallization and oxidation at high temperatures is confirmed by X-ray diffraction measurements. Pronounced changes in optical reflectance and sheet resistance are observed with temperature, in line with structural relaxation and change. The activation barriers for crystallization and oxidation are determined to be 1.01 eV and 0.83 eV, respectively, for FeCo-rich and Tb-rich samples. Better thermal stability against crystallization and oxidation is demonstrated in the FeCo-rich sample than the Tb-rich type. Our results provide some useful information for the alloy used in device fabrication.
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High particulate iron(II) content in glacially sourced dusts enhances productivity of a model diatom
Shoenfelt, Elizabeth M.; Sun, Jing; Winckler, Gisela; Kaplan, Michael R.; Borunda, Alejandra L.; Farrell, Kayla R.; Moreno, Patricio I.; Gaiero, Diego M.; Recasens, Cristina; Sambrotto, Raymond N.; Bostick, Benjamin C.
2017-01-01
Little is known about the bioavailability of iron (Fe) in natural dusts and the impact of dust mineralogy on Fe utilization by photosynthetic organisms. Variation in the supply of bioavailable Fe to the ocean has the potential to influence the global carbon cycle by modulating primary production in the Southern Ocean. Much of the dust deposited across the Southern Ocean is sourced from South America, particularly Patagonia, where the waxing and waning of past and present glaciers generate fresh glaciogenic material that contrasts with aged and chemically weathered nonglaciogenic sediments. We show that these two potential sources of modern-day dust are mineralogically distinct, where glaciogenic dust sources contain mostly Fe(II)-rich primary silicate minerals, and nearby nonglaciogenic dust sources contain mostly Fe(III)-rich oxyhydroxide and Fe(III) silicate weathering products. In laboratory culture experiments, Phaeodactylum tricornutum, a well-studied coastal model diatom, grows more rapidly, and with higher photosynthetic efficiency, with input of glaciogenic particulates compared to that of nonglaciogenic particulates due to these differences in Fe mineralogy. Monod nutrient accessibility models fit to our data suggest that particulate Fe(II) content, rather than abiotic solubility, controls the Fe bioavailability in our Fe fertilization experiments. Thus, it is possible for this diatom to access particulate Fe in dusts by another mechanism besides uptake of unchelated Fe (Fe′) dissolved from particles into the bulk solution. If this capability is widespread in the Southern Ocean, then dusts deposited to the Southern Ocean in cold glacial periods are likely more bioavailable than those deposited in warm interglacial periods. PMID:28691098
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Kerisit, Sebastien; Bylaska, Eric J; Massey, Michael S; McBriarty, Martin E; Ilton, Eugene S
2016-11-21
Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation states (VI, V, and IV) and charge compensation schemes were varied. Simulated trajectories were used to calculate the U L III -edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO 2 ), and constrained the S 0 2 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to addition of one electron into the solid (-1 H + , +1 e - ). The ability of AIMD to model higher energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with applications over a broad swath of chemistry and materials science.
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Tellurium Stable Isotopes as a Paleoredox Proxy
NASA Astrophysics Data System (ADS)
Wasserman, N.; Johnson, T. M.
2017-12-01
Despite arguments for variably-oxygenated shallow waters and anoxic deep marine waters, which delayed animal development until the Neoproterozoic Oxidation Event, the magnitude of atmospheric oxygen during the Proterozoic is still uncertain [1]. The evidence for low pO2 (<0.1-1% PAL) is based on geochemical and isotopic proxies, which track the mobilization of Fe and Mn on the continents. For example, large chromium isotope shifts occur at the Neoproterozoic Oxidation Event due to the initiation of Cr redox cycling, but this proxy is insensitive to fluctuations in the lower-pO2 conditions at other times during the Proterozoic. Tellurium, a metalloid with a lower threshold to oxidation, may be sensitive to pO2 shifts in a lower range. In the reduced forms, Te(-II) and Te(0), the element is insoluble and immobile. However, in the more oxidized phases, Te(IV) and Te(VI), Te can form soluble oxyanions (though it tends to adsorb to Fe-oxyhydroxides and clays) [2]. Te stable isotopes have been shown to fractionate during abiotic or biologic reduction of Te(VI) or Te(IV) to elemental Te(0) [3, 4]. Utilizing hydride generation MC-ICP-MS, we are able to obtain high precision (2σ 0.04‰) measurements of δ128Te/125Te for natural samples containing < 10 ng of Te. A suite of Phanerozoic and Proterozoic ironstones show significant variation in δ128Te/125Te (<0.5‰), suggesting that the Te redox cycle was active during the Proterozoic. Future directions will include Te isotope measurements of Precambrian paleosols to determine natural isotope variation before the Great Oxidation Event and experiments to determine fractionation during adsorption to Fe-oxyhydroxides. [1] Planavsky et al. (2014) Science 346 (6209), pp. 635-638 [2] Qin et al. (2017) Environmental Science and Technology 51 (11), pp 6027-6035 [3] Baesman et al. (2007) Applied Environmental Microbiology 73 (7), pp 2135-2143 [4] Smithers and Krause (1968) Canadian Journal of Chemistry 46(4): pp 583-591
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kerisit, Sebastien; Bylaska, Eric J.; Massey, Michael S.
2016-11-21
Incorporation of economically or environmentally consequential polyvalent metals into iron (oxyhydr)oxides has applications in environmental chemistry, remediation, and materials science. A primary tool for characterizing the local coordination environment of such metals, and therefore building models to predict their behavior, is extended X-ray absorption fine structure spectroscopy (EXAFS). Accurate structural information can be lacking, yet is required to constrain and inform data interpretation. In this regard, ab initio molecular dynamics (AIMD) was used to calculate the local coordination environment of minor amounts of U incorporated in the structure of goethite (α-FeOOH). U oxidation state (VI, V, and IV) and chargemore » compensation scheme (CCS) were varied. Simulated trajectories were used to calculate the U LIII-edge EXAFS function and fit experimental EXAFS data for U incorporated into goethite under reducing conditions. Calculations that closely matched the U EXAFS of the well-characterized mineral uraninite (UO2), and constrained the S02 parameter to be 0.909, validated the approach. The results for the U-goethite system indicated that U(V) substituted for structural Fe(III) in octahedral uranate coordination. Charge balance was achieved by the loss of one structural proton coupled to injection of one electron into the solid (–1 H+, + 1 e-). The ability of AIMD to model higher-energy states thermally accessible at room temperature is particularly relevant for protonated systems such as goethite, where proton transfers between adjacent octahedra had a dramatic effect on the calculated EXAFS. Vibrational effects as a function of temperature were also estimated using AIMD, allowing separate quantification of thermal and configurational disorder. In summary, coupling AIMD structural modeling and EXAFS experiments enables modeling of the redox behavior of polyvalent metals that are incorporated in conductive materials such as iron (oxyhydr)oxides, with applications over a broad swath of chemistry and materials science.« less
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Evolution of structural and magnetic properties of amorphous CoFeB film with thermal annealing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gupta, Ranjeeta; Gupta, Ajay; Gupta, Mukul
2013-08-14
Evolution of structural and magnetic properties of amorphous Co{sub 68}Fe{sub 14}B{sub 18} thin film with thermal annealing has been studied. Initially, the film exhibits a structural relaxation as evidenced by annihilation of excess free volume and an increase in topological short range order. Annealing at 473 K results in precipitation of primary phase followed by formation of boride phase at a still higher temperature of 598 K. Iron preferentially precipitates out in the primary phase, resulting in the formation of bcc Co{sub 58}Fe{sub 41}. This suggests an affinity of Co towards B. Such affinity between Co and B is evidencedmore » even in the as-deposited film, using hard x-ray photoelectron spectroscopy (HAXPES) measurements. As-deposited film exhibits an in-plane uniaxial magnetic anisotropy which disappears at a temperature well beyond crystallization temperature, suggesting that the origin of anisotropy is mainly a chemical short range order in the system. Variation in the coercivity with thermal annealing can be understood in terms of random anisotropy model. Precise measurement of Fe self-diffusion using neutron reflectivity shows that diffusion length associated with annihilation of excess free volume in the film is about 0.5 nm. This agrees with the length scale of structural fluctuations in amorphous alloys. Secondary ion mass spectrometry measurements show that thermal annealing results in depletion of B in the region of the interface with the substrate, with associated faster Fe diffusion in this region. This faster diffusion of Fe may be a possible cause of preferential crystallization of the film in the interfacial region as seen in some earlier studies.« less
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Smith, Kathleen S.; Ranville, James F.; Lesher, Emily K.; Diedrich, Daniel J.; McKnight, Diane M.; Sofield, Ruth M.
2014-01-01
This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on ,i>Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 μg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 μg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.
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NASA Astrophysics Data System (ADS)
Du, Jianghui; Haley, Brian A.; Mix, Alan C.
2016-11-01
The isotopic composition of neodymium (εNd) extracted from sedimentary Fe-Mn oxyhydroxide offers potential for reconstructing paleo-circulation, but its application depends on extraction methodology and the mechanisms that relate authigenic εNd to bottom water. Here we test methods to extract authigenic εNd from Gulf of Alaska (GOA) sediments and assess sources of leachate Nd, including potential contamination from trace dispersed volcanic ash. We show that one dominant phase is extracted via leaching of core-top sediments. Major and trace element geochemistry demonstrate that this phase is authigenic Fe-Mn oxyhydroxide. Contamination of leachate (authigenic) Nd from detrital sources is insignificant (<1%); our empirical results are consistent with established kinetic mineral dissolution rates and theory. Contamination of extracted εNd from leaching of volcanic ash is below analytical uncertainty. However, the εNd of core-top leachates in the GOA is consistently more radiogenic than bottom water. We infer that authigenic phases record pore water εNd, and the relationships of εNd among bottom waters, pore waters, authigenic phases and detrital sediments are primarily governed by the exposure time of bottom water to sea-floor sediments, rate of exchange across the sediment-water interface and the reactivity and composition of detrital sediments. We show that this conceptual model is applicable on the Pacific basin scale and provide a new framework to understand the role of authigenic phases in both modern and paleo-applications, including the use of authigenic εNd as a paleo-circulation tracer.
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Preparation, mechanical strengths, and thermal
NASA Astrophysics Data System (ADS)
Inoue, A.; Furukawa, S.; Hagiwara, M.; Masumoto, T.
1987-05-01
Ni-based amorphous wires with good bending ductility have been prepared for Ni75Si8B17 and Ni78P12B10 alloys containing 1 to 2 at. pct Al or Zr by melt spinning in rotating water. The enhancement of the wire-formation tendency by the addition of Al has been clarified to be due to the increase in the stability of the melt jet through the formation of a thin A12O3 film on the outer surface. The maximum wire diameter is about 190 to 200 μm for the Ni-Si (or P)-B-Al alloys and increases to about 250 μm for the Ni-Si-B-Al-Cr alloys containing 4 to 6 at. pct Cr. The tensile fracture strength and fracture elongation are 2730 MPa and 2.9 pct for (Ni0.75Si0.08B0.17 99Al1) wire and 2170 MPa and 2.4 pct for (Ni0.78P0.12B0.1)99Al1 wire. These wires exhibit a fatigue limit under dynamic bending strain in air with a relative humidity of 65 pct; this limit is 0.50 pct for a Ni-Si-B-Al wire, which is higher by 0.15 pct than that of a Fe75Si10B15 amorphous wire. Furthermore, the Ni-base wires do not fracture during a 180-deg bending even for a sample annealed at temperatures just below the crystallization temperature, in sharp contrast to high embrittlement tendency for Fe-base amorphous alloys. Thus, the Ni-based amorphous wires have been shown to be an attractive material similar to Fe- and Co-based amorphous wires because of its high static and dynamic strength, high ductility, high stability to thermal embrittlement, and good corrosion resistance.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Taghvaei, Amir Hossein, E-mail: Amirtaghvaei@gmail.com; Department of Materials Science and Engineering, Shiraz University of Technology, Shiraz; Stoica, Mihai
2014-06-01
The influence of ball milling on the atomic structure and magnetic properties of the Co{sub 40}Fe{sub 22}Ta{sub 8}B{sub 30} metallic glass with a high thermal stability and excellent soft magnetic properties has been investigated. After 14 h of milling, the obtained powders were found to consist mainly of an amorphous phase and a small fraction of the (Co,Fe){sub 21}Ta{sub 2}B{sub 6} nanocrystals. The changes in the reduced pair correlation functions suggest noticeable changes in the atomic structure of the amorphous upon ball milling. Furthermore, it has been shown that milling is accompanied by introduction of compressive and dilatational sites inmore » the glassy phase and increasing the fluctuation of the atomic-level hydrostatic stress without affecting the coordination number of the nearest neighbors. Ball milling has decreased the thermal stability and significantly affected the magnetic properties through increasing the saturation magnetization, Curie temperature of the amorphous phase and coercivity. - Highlights: • Ball milling affected the atomic structure of Co{sub 40}Fe{sub 22}Ta{sub 8}B{sub 30} metallic glass. • Mechanically-induced crystallization started after 4 h milling. • Milling increased the fluctuation of the atomic-level hydrostatic stress in glass. • Ball milling influenced the thermal stability and magnetic properties.« less
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NASA Astrophysics Data System (ADS)
Mitra, A.; Kim, H.-Y.; Louzguine, D. V.; Nishiyama, N.; Shen, B.; Inoue, A.
2004-07-01
Crystallisation behaviour and magnetic properties of as-spun and annealed Fe 40Co 40Cu 0.5Zr 9Al 2Si 4B 4.5 alloy have been studied. The annealing was performed at 873 K for 15 min. XRD and TEM studies shows the formation of nanocrystalline α-(Fe,Co)(SiAl) particles with 7.5±2 nm in diameter dispersed in an amorphous matrix. The Curie temperature of the as-spun amorphous ribbon is 736 K. Saturation magnetisation of the annealed sample decreases at a rate of 0.5 emu/g/K in the measured temperature range of 300-1000 K. Excellent room temperature AC magnetic properties are achieved for the nanocrystalline sample. The low value of the imaginary part of the permeability and the high cut-off frequency (20 kHz) suggest that the eddy current contribution in the annealed materials is low. The coercivity of the annealed sample remains almost constant at 95 A/m up to the frequency of 20 kHz. High saturation magnetisation, high Curie temperature and excellent soft magnetic properties in the nanocrystalline state suggests that Fe 40Co 40Cu 0.5Zr 9Al 2Si 4B 4.5 alloy is a strong candidate for high temperature magnetic application.
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Attenuation of dissolved metals in neutral mine drainage in the Zambian Copperbelt.
Sracek, Ondra; Filip, Jan; Mihaljevič, Martin; Kříbek, Bohdan; Majer, Vladimír; Veselovský, František
2011-01-01
Behaviour of metals like Cu and Co was studied in nearly neutral (pH ≥ 6.4) mine drainage seepage in a stream downgradient of a tailing dam at Chambishi site in the Copperbelt of Zambia. They are attenuated by precipitation of ferruginous ochres that incorporate significant quantities of metals. Using chemical analysis, X-ray powder diffraction and Mössbauer spectroscopy, we show that the ochres are composed mostly of amorphous ferric hydroxide. Close to the seepage face, the total Fe content of ochres increases due to precipitation of amorphous ferric hydroxide, but total Fe in sediment decreases further downstream. The stream then flows through wetland (dambo) where the remaining fraction of metals is removed. During rainy periods, increased flow rate may result in re-suspension of ochres, increasing thus the mobility of metals. Major ions like sulphate are conservative at the start of the dry period (May), but gypsum may probably precipitate later at the end of the dry period. Sequential extractions of bulk sediments indicate that Mn behaves differently to Fe, with a trend of increasing Mn with distance from the tailing dam. There is much more Fe than Mn in residual (Aqua Regia) fraction, indicating that amorphous ferric hydroxides are transformed to more crystalline phases deeper in sediment. Environmental impact of mine drainage is relatively limited due to its neutral character.
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The Mineralogy of Circumstellar Silicates Preserved in Cometary Dust
NASA Technical Reports Server (NTRS)
Keller, L. P.; Messenger, S.
2010-01-01
Interplanetary dust particles (IDPs) contain a record of the building blocks of the solar system including presolar grains, molecular cloud material, and materials formed in the early solar nebula. Cometary IDPs have remained relatively unaltered since their accretion because of the lack of parent body thermal and aqueous alteration. We are using coordinated transmission electron microscope (TEM) and ion microprobe studies to establish the origins of the various components within cometary IDPs. Of particular interest is the nature and abundance of presolar silicates in these particles because astronomical observations suggest that crystalline and amorphous silicates are the dominant grain types produced in young main sequence stars and evolved O-rich stars. Five circumstellar grains have been identified including three amorphous silicate grains and two polycrystalline aggregates. All of these grains are between 0.2 and 0.5 micrometers in size. The isotopic compositions of all five presolar silicate grains fall within the range of presolar oxides and silicates, having large (17)O-enrichments and normal (18)O/(16)O ratios (Group 1 grains from AGB and RG stars). The amorphous silicates are chemically heterogeneous and contain nanophase FeNi metal and FeS grains in a Mg-silicate matrix. Two of the amorphous silicate grains are aggregates with subgrains showing variable Mg/Si ratios in chemical maps. The polycrystalline grains show annealed textures (equilibrium grains boundaries, uniform Mg/Fe ratios), and consist of 50-100 nm enstatite and pyrrhotite grains with lesser forsterite. One of the polycrystalline aggregates contains a subgrain of diopside. The polycrystalline aggregates form by subsolidus annealing of amorphous precursors. The bulk compositions of the five grains span a wide range in Mg/Si ratios from 0.4 to 1.2 (avg. 0.86). The average Fe/Si (0.40) and S/Si (0.21) ratios show a much narrower range of values and are approximately 50% of their solar abundances. The latter observation may indicate a decoupling of the silicate and sulfide components in grains that condense in stellar outflows. The amorphous silicate grains described here were not extensively affected by irradiation, sputtering, or thermal processing and may represent relatively pristine circumstellar grains. They are strong candidates for the "dirty silicates" in astronomical observations of circumstellar dust shells. The polycrystalline grains were originally amorphous silicate grains that were likely annealed in the early solar nebula but the processing was not sufficient to erase their anomalous oxygen isotopic compositions.
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NASA Astrophysics Data System (ADS)
Dia, A.; Davranche, M.; Fakih, M.; Nowack, B.; Morin, G.; Gruau, G.
2009-04-01
Iron (III) oxides are ubiquitous components of soils, sediments, aquifers and geological materials. Trace metals associate with Fe (III) oxides as adsorbed or co-precipitated species and, consequently the biogeochemical cycles of Fe and trace metals are closely linked. Using a new monitoring tool recently developed, this study was dedicated to understand how do interplay biological and mineralogical (crystallographic and specific surface area) controls in the Fe oxyhydroxide reductive dissolution within soils and which can be the consequences on associated trace metal release. For this purpose, polymer slides covered by synthetic As-spiked ferrihydrite (As-Fh) or As-spiked lepidocrocite (As-Lp) were inserted into an organic-rich wetland soil in non conventional columns system under anaerobic conditions. This technique was developed to allow the insertion of slides into a structured soil without significant disturbance and to avoid the mechanical abrasion of oxides from slides that would occur in an equilibrium batch system under stirring. Slides were recovered after different periods of time to evaluate (i) the impact of (bio)reduction on both Fe-oxide dissolution and secondary mineral precipitation and, (ii) the subsequent effects on As mobility. XRF analyses of the slides were conducted before and after contact with the soil to determine the amount of Fe and associated As remaining on the slides. Fe(II), acetate, nitrate, sulphate and total metals of the soil solution was followed through time by ion chromatography and ICP-MS measurements. The important bacterial colonization and occurrence of biofilm evidenced by SEM analyses of the slides suggested the presence of biologically mediated processes. As previously shown elsewhere the kinetics of the suspected occurring bacterial reduction differ significantly from abiotic reduction data from literature. The important point is that conversely to what has been observed in published experimental data, the dissolution rates remained here fairly constant through time since the organic matter present in the interacting solution complexed the released Fe(II), which was therefore not able to accumulate onto the bacterial cell surfaces. The organic matter mediated complexation of Fe(II) prevented thus the progressive inhibition of the enzymatic reduction to occur as elsewhere evidenced with other experimental conditions. As expected, the reductive dissolution of the less crystallized ferrihydrite started quicker than that of lepidocrocite. The newly formed minerals were mostly composed of Fe-sulphides. Iron(II) complexation by organic molecules in solution likely prevented formation of secondary Fe(II, III)-rich minerals. The relative proportion of As(III) increased with time on the As-Fh slides, and was combined with a decrease of the Fe/As ratio, suggesting a partial adsorption of As(III) onto minerals. By contrast, for lepidocrocite, the Fe/As ratio increased, suggesting that As(III) was less readsorbed due the lower available site number and the deletion of As adsorption sites on the reduced lepidocrocite surface. Only a weak proportion of As(III) was sequestered by readsorption onto unreduced Fe-oxides and possibly on secondary Fe-sulphide minerals, especially when the iron oxide had a low surface area. Therefore, wetlands and their waterlogged soils could be a non negligible source of As within soils, migrating first through soil solutions and then to the whole hydrosystem.
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Chen, Chunmei; Thompson, Aaron
2018-01-16
Abiotic Fe(II) oxidation by O 2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al 2 O 3 ) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO 2 at pH 6. We tracked Fe dynamics by adding 57 Fe(II) to 56 Fe-labeled goethite and γ-Al 2 O 3 and characterized the resulting solids using 57 Fe Mössbauer spectroscopy. We found Fe(II) oxidation was slower at low pO 2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II) (aq) alone, both goethite and γ-Al 2 O 3 surfaces increased Fe(II) oxidation rates regardless of pO 2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al 2 O 3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe(II) aq alone favored lepidocrocite. SRFA reduced oxidation rates in all treatments except the mineral-free systems at 21% pO 2 , and SRFA decreased Fe(III) phase crystallinity, facilitating low-crystalline ferrihydrite in the absence of mineral sorbents, low-crystalline lepidocrocite in the presence of γ-Al 2 O 3 , but either crystalline goethite or ferrihydrite when goethite was present. This work highlights that the oxidation rate, the types of mineral surfaces, and OM control Fe(III) precipitate composition.
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Structural Transformation in Fe73.5Nb3Cu1Si15.5B7 Amorphous Alloy Induced by Laser Heating
NASA Astrophysics Data System (ADS)
Nykyruy, Yu. S.; Mudry, S. I.; Kulyk, Yu. O.; Zhovneruk, S. V.
2018-03-01
The effect of continuous laser irradiation (λ = 1.06 μm) with laser power of 45 W on the structure of Fe73.5Nb3Cu1Si15.5B7 amorphous alloy has been studied using X-ray diffraction and SEM methods. The sample of the ribbon has been placed at a distance from the focal plane of the lens, so a laser beam has been defocused and the diameter of laser spot on the ribbon surface has been about 10 mm. An exposure time τ varied within interval 0.25-0.70 s. Under such conditions structural transformation processes, which depend on the exposure time, have occurred in an irradiated zone. Crystallization process has started at τ = 0.35 s with the formation of α-Fe(Si) nanocrystalline phase, while complete crystallization has occurred at τ = 0.55 s with formation of two nanocrystalline phases: α-Fe(Si) and a hexagonal H-phase.
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OPTICAL AND SPECTROSCOPIC STUDIES OF Fe2O3-Bi2O3-B2O3:V2O5 GLASSES
NASA Astrophysics Data System (ADS)
Sanjay; Kishore, N.; Agarwal, A.; Dahiya, S.; Pal, Inder; Kumar, Navin
2013-11-01
The glasses of compositions xFe2O3ṡ (40 - x)Bi2O3ṡ60B2O3ṡ2V2O5 have been prepared by the standard melt-quenching technique. Amorphous nature of these samples is ascertained by XRD patterns. The presence of BO3 and BO4 units is identified by IR spectra of glass samples. The absorption edge (λcut-off) shifts toward longer wavelengths with an increase in Fe2O3 content in the glass matrix. The values of optical band gap energy for indirect allowed and forbidden transitions have been determined and it is found to decrease with increase in transition metal ions. The Urbach's energy is used to characterize the degree of disorder in amorphous solids.
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Deposition-temperature dependence of structural anisotropy in amorphous Tb-Fe films
NASA Astrophysics Data System (ADS)
Harris, V. G.; Elam, W. T.; Koon, N. C.; Hellman, F.
1994-02-01
The anisotropic local structure in a series of amorphous Tb26Fe74 films deposited at different deposition temperatures and having different magnetic anisotropy energies have been investigated using polarization-dependent extended x-ray-absorption fine-structure measurements. Samples deposited at temperatures >=300 K exhibit anisotropic pair correlations where like atomic pairs are favored in plane and unlike pairs are favored out of plane. Both the anisotropic pair correlations and the perpendicular magnetic anisotropy increase with increasing deposition temperature. In contrast, a sample deposited at 77 K was found to have isotropic pair correlations, low perpendicular magnetic anisotropy, and a large (~=1%) in-plane compression.
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NASA Astrophysics Data System (ADS)
Lashgari, H. R.; Cadogan, J. M.; Kong, C.; Tang, C.; Doherty, C.; Chu, D.; Li, S.
2018-06-01
In the present study, the effect of stress-relaxation treatment (Tstress-relaxation < Tglass transition) on the magnetic texture, nanomechanical properties, and variation of free-volume in FeSiBNb amorphous alloy was investigated using Mössbauer spectroscopy, nanoindentation, dynamic mechanical analysis (DMA), and positron annihilation lifetime spectroscopy (PALS) techniques. It was shown that stress-relaxation treatment slightly improved the magnetic texture by 6% at T ≪Tg due to small-scale displacement of atoms whereas the magnetic texture was deteriorated due to thermal treatment at temperatures around the glass transition point (large-scale displacement of atoms). According to nanoindentation results, the hardness (H) and reduced modulus (Er) of the amorphous ribbon increased by 15% and 13%, respectively, after stress-relaxation treatment at 716 K for 5 min. Increasing the stress-relaxation time from 5 min to 60 min at 716 K resulted in decreases in the hardness and reduced modulus which are attributed to the increase of free-volume defects (increase of τ2 lifetime measured by PALS). Transmission electron microscopy (TEM) showed the formation of extremely fine embryos of α-Fe (3-5 nm in size) after stress-relaxation treatment.
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NASA Astrophysics Data System (ADS)
Lu, Qiang; Liu, Li; Yang, Shuanglei; Liu, Jun; Tian, Qingyong; Yao, Weijing; Xue, Qingwen; Li, Mengxiao; Wu, Wei
2017-09-01
More convenience and intelligence life lead by flexible/wearable electronics requires innovation and hommization of power sources. Here, amorphous FeOOH/MnO2 composite as screen-printed electrode materials for supercapacitors (SCs) is synthesized by a facile method, and solid-state flexible SCs with aesthetic design are fabricated by fully screen-printed process on different substrates, including PET, paper and textile. The amorphous FeOOH/MnO2 composite shows a high specific capacitance and a good rate capability (350.2 F g-1 at a current density of 0.5 A g-1 and 159.5 F g-1 at 20 A g-1). It also possesses 95.6% capacitance retention even after 10 000 cycles. Moreover, the all-printed solid-state flexible SC device exhibits a high area specific capacitance of 5.7 mF cm-2 and 80% capacitance retention even after 2000 cycles. It also shows high mechanical flexibility. Simultaneously, these printed SCs on different substrates in series are capable to light up a 1.9 V yellow light emitting diode (LED), even after bending and stretching.
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The magnetic properties of a magnetic detector using oxidized amorphous Co 95- xFe 5(BSi) x alloys
NASA Astrophysics Data System (ADS)
Ahn, S. J.; Kim, C. K.; Kim, S. J.; Choi, D. K.; O'Handley, R. C.
2000-07-01
A comparative oxidation study of several amorphous Co 75- xFe 5(BSi) 20+ x alloys was carried out. Reentrant magnetization behavior and field-induced anisotropy which are of a critical importance for a magnetic detector were obtained after oxidation of the amorphous Co-rich ribbons. During this oxidation, the ribbons develop surface oxides which are primarily nonmagnetic borosilicate or a combination of borosilicate and magnetic oxides such CoO or FeO. Beneath this lies a 100-1000 Å thick Co-rich magnetic alloy which may be either HCP or FCC in its crystal structure. The thickness of the Co-crystallized layer is determined by the type of the surface oxides. The oxidation products such as appear to affect the reentrant magnetization behavior of Co-rich amorphous alloys significantly. We have determined the amount of metalloids (a critical concentration of B and Si) which is necessary to form a continuous layer of the most thermodynamically stable oxide, in our case borosilicate, on the surface. We also observed that there is a good correlation between reentrant magnetization and the thickness of Co layer. The best reentrant M- H loop for the magnetic detector was obtained in ribbons with a surface borate-rich borosilicate since it ensures conditions such as (1) metalloid depletion in the substrate and (2) formation of oxygen impurity faults in Co grains that are required for strong reentrant magnetization behavior.
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NASA Astrophysics Data System (ADS)
Schwarz, B.; Rossi, P. J.; Straßberger, L.; Jörg, F.; Meka, S. R.; Bischoff, E.; Schacherl, R. E.; Mittemeijer, E. J.
2014-09-01
Specimens of iron-based binary Fe-Si alloy and ternary Fe-Me-Si alloys (with Me = Ti, Cr and V) were nitrided at 580 °C in a NH3/H2-gas mixture applying a nitriding potential of 0.1 atm-1/2 until nitrogen saturation in the specimens was attained. In contrast with recent observations in other Fe-Me1-Me2 alloys, no "mixed" (Me1, Me2) nitrides developed in Fe-Me-Si alloys upon nitriding: first, all Me precipitates as MeN; and thereafter, all Si precipitates as Si3N4. The MeN precipitates as crystalline, finely dispersed, nanosized platelets, obeying a Baker-Nutting orientation relationship (OR) with respect to the ferrite matrix. The Si3N4 precipitates as cubically, amorphous particles; the incoherent (part of the) MeN/α-Fe interface acts as heterogeneous nucleation site for Si3N4. The Si3N4-precipitation rate was found to be strongly dependent on the degree of coherency of the first precipitating MeN. The different, even opposite, kinetic effects observed for the various Fe-Me-Si alloys could be ascribed to the different time dependences of the coherent → incoherent transitions of the MeN particles in the different Fe-Me-Si alloys.
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Liu, Zhao-Dong; Wang, Hai-Cui; Zhou, Qin; Xu, Ren-Kou
2017-11-01
Iron (Fe) and aluminum (Al) hydroxides in variable charge soils attached to rice roots may affect surface-charge properties and subsequently the adsorption and uptake of nutrients and toxic metals by the roots. Adhesion of amorphous Fe and Al hydroxides onto rice roots and their effects on zeta potential of roots and adsorption of potassium (K + ) and cadmium (Cd 2+ ) by roots were investigated. Rice roots adsorbed more Al hydroxide than Fe hydroxide because of the greater positive charge on Al hydroxide. Adhesion of Fe and Al hydroxides decreased the negative charge on rice roots, and a greater effect of the Al hydroxide. Consequently, adhesion of Fe and Al hydroxides reduced the K + and Cd 2+ adsorption by rice roots. The results of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and desorption of K + and Cd 2+ from rice roots indicated that physical masking by Fe and Al hydroxides and diffuse-layer overlapping between the positively-charged hydroxides and negatively-charged roots were responsible for the reduction of negative charge on roots induced by adhesion of the hydroxides. Therefore, the interaction between Fe and Al hydroxides and rice roots reduced negative charge on roots and thus inhibited their adsorption of nutrient and toxic cations. Copyright © 2017 Elsevier Inc. All rights reserved.
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Stabilisation of Ce-Cu-Fe amorphous alloys by addition of Al
NASA Astrophysics Data System (ADS)
Kelhar, Luka; Ferčič, Jana; Boulet, Pascal; Maček-Kržmanc, Marjeta; Šturm, Sašo; Lamut, Martin; Markoli, Boštjan; Kobe, Spomenka; Dubois, Jean-Marie
2016-10-01
The present work describes the formation of amorphous alloys in the (Al1-xCex)62Cu25Fe13 quaternary system (0 ≤ x ≤ 1). When the amount of Ce falls in the range 0.67 ≤ x ≤ 0.83, the alloys obtained exhibit a completely amorphous structure confirmed by powder X-ray diffraction. Otherwise, at compositions x = 0.5, 0.58, 0.92 and 1, a primary crystalline phase forms together with an amorphous matrix. The crystallisation temperature (Tx) decreases with increasing Ce content, varying from 593 K for x = 0.5-383 K for x = 1. Composition x = 0.75 is considered as the best glass former, exhibiting a large supercooled liquid region of 40 K width that precedes crystallisation. In order to form bulk amorphous alloys, ribbons with this later composition were consolidated into few millimetre thick discs using pulsed electric current sintering at different temperatures, yet preserving the amorphous structure. Meanwhile, increasing temperature above 483 K triggers crystallisation of a primary phase isostructural to AlCe3. Further increase in the temperature up to 573 K yields a higher fraction of the crystalline phase. Testing mechanical properties, using nanoindentation, revealed that both elastic modulus (E) and hardness (H) depend on the Al content, ranging from E = 85.6 ± 3.7 GPa and H = 6.2 ± 0.7 GPa for x = 0.5 down to E = 39.8 ± 1.0 GPa and H = 3.1 ± 0.2 GPa for x = 0.92.
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Ion beam irradiation of lanthanum and thorium-doped yttrium titanates
NASA Astrophysics Data System (ADS)
Lian, J.; Zhang, F. X.; Peters, M. T.; Wang, L. M.; Ewing, R. C.
2007-05-01
Y2Ti2O7 pyrochlores doped with La have been sintered at 1373 K for 12 h with the designed compositions of the (LaxY1-x)2Ti2O7 system (x = 0, 0.08, 0.5, and 1), and the phase compositions were analyzed by X-ray diffraction. Limited amounts of La were incorporated into yttrium titanate pyrochlore structure for La-doped samples; while, the end member composition of La2Ti2O7 formed a layered perovskite structure. Ion beam-induced amorphization occurred for all compositions in the (LaxY1-x)2Ti2O7 binary under 1 MeV Kr2+ irradiation at room temperature, and the critical amorphization dose decreased with increasing amounts of La3+. The critical amorphization temperatures for Y2Ti2O7, (La0.162Y0.838)2Ti2O7 and La2Ti2O7 were determined to be ∼780, 890 and 920 K, respectively. Th4+ and Fe3+-doped yttrium titanate pyrochlores were synthesized at 1373 K by sintering Y2Ti2O7 with (ThO2 + Fe2O3). Pyrochlore structures and the chemical compositions were primarily identified by the X-ray diffraction and energy dispersive X-ray (EDX) measurements. The lattice parameter and the critical amorphization dose (1 MeV Kr2+ at room temperature) increase for yttrium titanate pyrochlores with the addition of Th. The increasing 'resistance' to amorphization with less La and greater Th and Fe contents for (Y1-xLax)2Ti2O7 and Y2Ti2O7-Fe2O3-ThO2 systems, respectively, are consistent with the changes in the average ionic radius ratio at the A-sites and B-sites. These results suggest that the addition of lanthanides and actinides (e.g., Th, U, or Pu) will affect the structural stability, as well as the radiation response behavior of the pyrochlore structure-type.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Smith, Frances N.; Um, Wooyong; Taylor, Christopher D.
2016-05-17
Iron oxides and oxyhydroxides play an important role in minimizing the mobility of redox-sensitive elements in engineered and natural environments. For the radionuclide technetium-99 (Tc), these phases hold promise as primary hosts for increasing Tc loading into glass waste form matrices, or as secondary sinks during the long-term storage of nuclear materials. Recent experiments show that the inverse spinel, magnetite [Fe(II)Fe(III)2O4], can incorporate Tc(IV) into its octahedral sub-lattice, and in that same class of materials, trevorite [Ni(II)Fe(III)2O4] is also being investigated for its ability to host Tc(IV). However, questions remain regarding the most energetically favorable charge-compensation mechanism for Tc(IV) incorporationmore » in each structure, which will affect Tc behavior under changing waste processing or storage conditions. Here, quantum-mechanical methods were used to evaluate incorporation energies and optimized lattice bonding environments for three different, charge-balanced Tc(IV) incorporation mechanisms in magnetite and trevorite. In both cases, the removal of two octahedral Fe(II) or Ni(II) ions upon the addition of Tc(IV) to an octahedral site is the most stable mechanism, relative to the creation of octahedral Fe(III) defects or increasing octahedral Fe(II) content. Following hydration-energy corrections, Tc(IV) incorporation into magnetite is energetically favorable while an energy barrier exists for trevorite.« less
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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
2014-01-01
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.
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Aral, Gurcan; Islam, Md Mahbubul; Wang, Yun-Jiang; Ogata, Shigenobu; Duin, Adri C T van
2018-06-14
To avoid unexpected environmental mechanical failure, there is a strong need to fully understand the details of the oxidation process and intrinsic mechanical properties of reactive metallic iron (Fe) nanowires (NWs) under various aqueous reactive environmental conditions. Herein, we employed ReaxFF reactive molecular dynamics (MD) simulations to elucidate the oxidation of Fe NWs exposed to molecular water (H2O) and hydrogen peroxide (H2O2) environment, and the influence of the oxide shell layer on the tensile mechanical deformation properties of Fe NWs. Our structural analysis shows that oxidation of Fe NWs occurs with the formation of different iron oxide and hydroxide phases in the aqueous molecular H2O and H2O2 oxidizing environments. We observe that the resulting microstructure due to pre-oxide shell layer formation reduces the mechanical stress via increasing the initial defect sites in the vicinity of the oxide region to facilitate the onset of plastic deformation during tensile loading. Specifically, the oxide layer of Fe NWs formed in the H2O2 environment has a relatively significant effect on the deterioration of the mechanical properties of Fe NWs. The weakening of the yield stress and Young modulus of H2O2 oxidized Fe NWs indicates the important role of local oxide microstructures on mechanical deformation properties of individual Fe NWs. Notably, deformation twinning is found as the primary mechanical plastic deformation mechanism of all Fe NWs, but it is initially observed at low strain and stress level for the oxidized Fe NWs.
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Chabaux, F.; O'Nions, R. K.; Cohen, A.S.; Hein, J.R.
1997-01-01
A detailed TIMS study of (234Uexc/238U), (230Th/232Th), and Th/U ratios have been performed on the outermost margin of ten hydrogenous Fe-Mn crusts from the equatorial Pacific Ocean and west-central Indian Ocean. Th/U concentration ratios generally decrease from the crust's surface down to 0.5-1 mm depth and growth rates estimated by uranium and thorium isotope ratios are significantly different in Fe-Mn crusts from the Peru Basin and the west-central Indian Ocean. Fe-Mn crusts from the same geographical area define a single trend in plots of Ln (234Uexc/238U) vs. Ln(230Th/232Th) and Th/U ratios vs. age of the analysed fractions. Results suggest that (1) hydrogenous Fe-Mn crusts remain closed-systems after formation, and consequently (2) the discrepancy observed between the 230Th and 234U chronometers in Fe-Mn crusts, and the variations of the Th/U ratios through the margin of Fe-Mn crusts, are not due to redistribution of uranium and thorium isotopes after oxyhydroxide precipitation, but rather to temporal variations of both Th/U and initial thorium activity ratios recorded by the Fe-Mn layers. Implications of these observations for determination of Fe-Mn crust growth-rates are discussed. Variations of both Th/U and initial Th activity ratios in Fe-Mn crusts might be related to changes in particle input to seawater and/or changes in ocean circulation during the last 150 ka. Copyright ?? 1997 Elsevier Science Ltd.
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Magnetic domain interactions of Fe3O4 nanoparticles embedded in a SiO2 matrix.
Fuentes-García, J A; Diaz-Cano, A I; Guillen-Cervantes, A; Santoyo-Salazar, J
2018-03-23
Currently, superparamagnetic functionalized systems of magnetite (Fe 3 O 4 ) nanoparticles (NPs) are promising options for applications in hyperthermia therapy, drug delivery and diagnosis. Fe 3 O 4 NPs below 20 nm have stable single domains (SSD), which can be oriented by magnetic field application. Dispersion of Fe 3 O 4 NPs in silicon dioxide (SiO 2 ) matrix allows local SSD response with uniaxial anisotropy and orientation to easy axis, 90° <001> or 180° <111>. A successful, easy methodology to produce Fe 3 O 4 NPs (6-17 nm) has been used with the Stöber modification. NPs were embedded in amorphous and biocompatible SiO 2 matrix by mechanical stirring in citrate and tetraethyl orthosilicate (TEOS). Fe 3 O 4 NPs dispersion was sampled in the range of 2-12 h to observe the SiO 2 matrix formation as time function. TEM characterization identified optimal conditions at 4 h stirring for separation of SSD Fe 3 O 4 in SiO 2 matrix. Low magnetization (M s ) of 0.001 emu and a coercivity (H c ) of 24.75 Oe indicate that the embedded SSD Fe 3 O 4 in amorphous SiO 2 reduces the M s by a diamagnetic barrier. Magnetic force microscopy (MFM) showed SSD Fe 3 O 4 of 1.2 nm on average embedded in SiO 2 matrix with uniaxial anisotropy response according to Fe 3+ and Fe 2+ electron spin coupling and rotation by intrinsic Neél contribution.
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NASA Astrophysics Data System (ADS)
2018-05-01
The main reactions considered in OM mineralization during early diagenesis of sediment are listed in Table 1. Under oxidant-depleted conditions, fermentation of metabolizable OM of general formula CxHyOz can yield acetate, CO2 and H2 (r1). Note that reaction r1 takes into account any source of CO2 during fermentation including the partial degradation of high molecular weight OM (HMW OM) into lower molecular weight OM (LMW OM; Corbett et al., 2013; Corbett et al., 2015). The products of this reaction yield CH4 via either acetate fermentation (r2) or hydrogenotrophy (r3). In addition, when electron acceptors (EAs), i.e., Fe(III), SO42-, and partially oxidized HS, are present, CH4 (r4) and OM (r5) can be oxidized to produce CO2. Here, nitrate and Mn oxyhydroxides were not considered as oxidants, owing to the very low concentration of the former (<2 μmol L-1) over the whole sampling interval and because Mn oxyhydroxides do not form under the slightly acidic conditions prevailing in these porewaters (Chappaz et al., 2008). In addition, we neglected precipitation and dissolution of carbonate minerals except for siderite precipitation (r6) due to its positive SI values (SI ≥ 0.5).
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Edwards, Katrina J; Glazer, B T; Rouxel, O J; Bach, W; Emerson, D; Davis, R E; Toner, B M; Chan, C S; Tebo, B M; Staudigel, H; Moyer, C L
2011-01-01
A novel hydrothermal field has been discovered at the base of Lōihi Seamount, Hawaii, at 5000 mbsl. Geochemical analyses demonstrate that ‘FeMO Deep', while only 0.2 °C above ambient seawater temperature, derives from a distal, ultra-diffuse hydrothermal source. FeMO Deep is expressed as regional seafloor seepage of gelatinous iron- and silica-rich deposits, pooling between and over basalt pillows, in places over a meter thick. The system is capped by mm to cm thick hydrothermally derived iron-oxyhydroxide- and manganese-oxide-layered crusts. We use molecular analyses (16S rDNA-based) of extant communities combined with fluorescent in situ hybridizations to demonstrate that FeMO Deep deposits contain living iron-oxidizing Zetaproteobacteria related to the recently isolated strain Mariprofundus ferroxydans. Bioenergetic calculations, based on in-situ electrochemical measurements and cell counts, indicate that reactions between iron and oxygen are important in supporting chemosynthesis in the mats, which we infer forms a trophic base of the mat ecosystem. We suggest that the biogenic FeMO Deep hydrothermal deposit represents a modern analog for one class of geological iron deposits known as ‘umbers' (for example, Troodos ophilolites, Cyprus) because of striking similarities in size, setting and internal structures. PMID:21544100
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Ziegler, Brady A.; McGuire, Jennifer T.; Cozzarelli, Isabelle M.
2015-01-01
Biodegradation of organic matter, including petroleum-based fuels and biofuels, can create undesired secondary water-quality effects. Trace elements, especially arsenic (As), have strong adsorption affinities for Fe(III) (oxyhydr)-oxides and can be released to groundwater during Fe-reducing biodegradation. We investigated the mobilization of naturally occurring As, cobalt (Co), chromium (Cr), and nickel (Ni) from wetland sediments caused by the introduction of benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol mixtures under iron- and nitrate-reducing conditions, using in situ push–pull tests. When BTEX alone was added, results showed simultaneous onset and similar rates of Fe reduction and As mobilization. In the presence of ethanol, the maximum rates of As release and Fe reduction were higher, the time to onset of reaction was decreased, and the rates occurred in multiple stages that reflected additional processes. The concentration of As increased from <1 μg/L to a maximum of 99 μg/L, exceeding the 10 μg/L limit for drinking water. Mobilization of Co, Cr, and Ni was observed in association with ethanol biodegradation but not with BTEX. These results demonstrate the potential for trace-element contamination of drinking water during biodegradation and highlight the importance of monitoring trace elements at natural and enhanced attenuation sites.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Takeuchi, A., E-mail: takeuchi@imr.tohoku.ac.jp; Zhang, Y.; Takenaka, K.
2015-05-07
Fe-based Fe{sub 85}B{sub 15}, Fe{sub 84}B{sub 15}Cu{sub 1}, Fe{sub 82}Si{sub 2}B{sub 15}Cu{sub 1}, Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, and Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} (NANOMET{sup ®}) alloys were experimental and computational analyzed to clarify the features of NANOMET that exhibits high saturation magnetic flux density (B{sub s}) nearly 1.9 T and low core loss than conventional nanocrystalline soft magnetic alloys. The X-ray diffraction analysis for ribbon specimens produced experimentally by melt spinning from melts revealed that the samples were almost formed into an amorphous single phase. Then, the as-quenched samples were analyzed with differential scanning calorimeter (DSC) experimentally for exothermicmore » enthalpies of the primary and secondary crystallizations (ΔH{sub x1} and ΔH{sub x2}) and their crystallization temperatures (T{sub x1} and T{sub x2}), respectively. The ratio ΔH{sub x1}/ΔH{sub x2} measured by DSC experimentally tended to be extremely high for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy, and this tendency was reproduced by the analysis with commercial software, Thermo-Calc, with database for Fe-based alloys, TCFE7 for Gibbs free energy (G) assessments. The calculations exhibit that a volume fraction (V{sub f}) of α-Fe tends to increase from 0.56 for the Fe{sub 85}B{sub 15} to 0.75 for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy. The computational analysis of the alloys for G of α-Fe and amorphous phases (G{sub α-Fe} and G{sub amor}) shows that a relationship G{sub α-Fe} ∼ G{sub amor} holds for the Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, whereas G{sub α-Fe} < G{sub amor} for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy at T{sub x1} and that an extremely high V{sub f} = 0.75 was achieved for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy by including 2.8 at. % Si and 4.5 at. % P into α-Fe. These computational results indicate that the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy barely forms amorphous phase, which, in turn, leads to high V{sub f} and resultant high B{sub s}.« less
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Kadirova, Zukhra C; Hojamberdiev, Mirabbos; Katsumata, Ken-Ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Sharipov, Khasan; Okada, Kiyoshi
2014-01-01
The spherical granular activated carbon-carbon composites (GAC-Fe) with different iron oxide contents (Fe mass% = 0.6-10) were prepared by a pore volume impregnation method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2-adsorption results confirm the presence of amorphous iron oxide, pyrolytic carbon, and graphitized globular carbon nanoparticles covered with amorphous carbon in the CAG-Fe. The rate of photodegradation of methylene blue (MB) in aqueous solution under UV light in the presence of oxalic acid correlates with porosity of the prepared materials. The total MB removal includes the combination of adsorption and photodegradation without the addition of H2O2. The results of total organic carbon (TOC) analysis reveal that the decolorization of MB in aqueous solution containing oxalic acid corresponds to the decomposition of organic compounds to CO2 and H2O.
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NASA Astrophysics Data System (ADS)
Mohri, K.; Takeuchi, S.
1982-11-01
New sensitive magnetic-field sensors are presented using twisted amorphous magnetostrictive ribbons such as Fe80B20 and Fe81-xCrxB17Si2. Sharp voltage pulses are induced between ends of the ribbon of as short as 25 mm or at the terminals of the detecting coil against external fields of as low as 1 Oe and 0.01 Hz-6 kHz. The domain nucleation field at the bistable flux reversal is very constant for 130 °C, 600 h using Fe79Cr2B17Si2, and a possible maximum operating temperature is about 180 °C. Small sized magnetic sensors without any windings for detecting rotational speed, distance, and other mechanical quantities are realized using the twisted ribbons by combining with small magnets. These sensitive and reliable magnetic sensors with digital outputs are suitable for applications in industrial robots and automobiles controlled with microcomputers.
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Arsenopyrite weathering under conditions of simulated calcareous soil.
Lara, René H; Velázquez, Leticia J; Vazquez-Arenas, Jorge; Mallet, Martine; Dossot, Manuel; Labastida, Israel; Sosa-Rodríguez, Fabiola S; Espinosa-Cristóbal, León F; Escobedo-Bretado, Miguel A; Cruz, Roel
2016-02-01
Mining activities release arsenopyrite into calcareous soils where it undergoes weathering generating toxic compounds. The research evaluates the environmental impacts of these processes under semi-alkaline carbonated conditions. Electrochemical (cyclic voltammetry, chronoamperometry, EIS), spectroscopic (Raman, XPS), and microscopic (SEM, AFM, TEM) techniques are combined along with chemical analyses of leachates collected from simulated arsenopyrite weathering to comprehensively examine the interfacial mechanisms. Early oxidation stages enhance mineral reactivity through the formation of surface sulfur phases (e.g., S n (2-)/S(0)) with semiconductor properties, leading to oscillatory mineral reactivity. Subsequent steps entail the generation of intermediate siderite (FeCO3)-like, followed by the formation of low-compact mass sub-micro ferric oxyhydroxides (α, γ-FeOOH) with adsorbed arsenic (mainly As(III), and lower amounts of As(V)). In addition, weathering reactions can be influenced by accessible arsenic resulting in the formation of a symplesite (Fe3(AsO4)3)-like compound which is dependent on the amount of accessible arsenic in the system. It is proposed that arsenic release occurs via diffusion across secondary α, γ-FeOOH structures during arsenopyrite weathering. We suggest weathering mechanisms of arsenopyrite in calcareous soil and environmental implications based on experimental data.
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The formation of magnetite in the early Archean oceans
NASA Astrophysics Data System (ADS)
Li, Yi-Liang; Konhauser, Kurt O.; Zhai, Mingguo
2017-05-01
Banded iron formations (BIFs) are iron- and silica-rich chemical sedimentary rocks that were deposited throughout much of the Precambrian. The biological oxidation of dissolved Fe(II) led to the precipitation of a ferric oxyhydroxide phase, such as ferrihydrite, in the marine photic zone. Upon burial, ferrihydrite was either transformed into hematite through dehydration or it was reduced to magnetite via biological or abiological Fe(III) reduction coupled to the oxidation of buried microbial biomass. However, it has always been intriguing as to why the oldest BIFs are characteristically magnetite-rich, while BIFs formed after the Neoarchean are dominated by hematite. Here, we propose that some magnetite in early Archean BIF could have precipitated directly from seawater through the reaction of settling ferrihydrite and hot, Fe(II)-rich hydrothermal fluids that existed in the deeper waters. We conducted experiments that showed the reaction of Fe(II) with biogenic ferric iron mats under strict anoxic conditions lead to the formation of a metastable green rust phase that within hours transformed into magnetite. Our model further posits that with the progressive cooling and oxidation of the Earth's oceans, the above reaction shuts off, and magnetite was subsequently restricted to reactions associated with diagenesis and metamorphism.
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Tunable Amorphous Photonic Materials with Pigmentary Colloidal Nanostructures
Han, Jinkyu; Lee, Elaine; Dudoff, Jessica K.; ...
2017-01-31
Amorphous photonic structures using pigmentary α-Fe 2O 3/SiO 2 core–shell nanoparticles are succesfully fabricated. The resulting non-iridicent brilliant colors can be manipulated by shell thickness, particle concentration, and external electrical stimuli using electrophoretic deposition process. In conclusion, fully reversible and instantaneous color changes as well as noticeable difference between transmitted and reflected colors is observed.