Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

2015-09-01

Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm-2 at a scan rate of 5 mV s-1. This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ˜90% after 5000 charge/discharge cycles at 7.5 mA cm-2. All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

Molecular orbital (SCF-X-α-SW) theory of Fe2+-Mn3+, Fe3+-Mn2+, and Fe3+-Mn3+ charge transfer and magnetic exchange in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1990-01-01

Metal-metal charge-transfer and magnetic exchange interactions have important effects on the optical spectra, crystal chemistry, and physics of minerals. Previous molecular orbital calculations have provided insight on the nature of Fe2+-Fe3+ and Fe2+-Ti4+ charge-transfer transitions in oxides and silicates. In this work, spin-unrestricted molecular orbital calculations on (FeMnO10) clusters are used to study the nature of magnetic exchange and electron delocalization (charge transfer) associated with Fe3+-Mn2+, Fe3+-Mn3+, and Fe2+-Mn3+ interactions in oxides and silicates. 

Biological regeneration of manganese (IV) and iron (III) for anaerobic metal oxide-mediated removal of pharmaceuticals from water.

PubMed

Liu, Wenbo; Langenhoff, Alette A M; Sutton, Nora B; Rijnaarts, Huub H M

2018-05-18

Applying manganese(IV)- or iron(III)-(hydr)oxides to remove pharmaceuticals from water could be attractive, due to the capacity of these metal oxides to remove pharmaceuticals and be regenerated. As pharmaceutical removal under anaerobic conditions is foreseen, Mn(IV) or Fe(III) regeneration under anaerobic conditions, or with minimum oxygen dosage, is preferred. In this study, batch experiments are performed to investigate (1) Mn(IV) and Fe(III) regeneration from Mn(II) and Fe(II); (2) the pharmaceutical removal during biological Mn(IV) and Fe(III) regeneration; and (3) anaerobic abiotic pharmaceutical removal with different Mn(IV) or Fe(III) species. Results show that biological re-oxidation of reduced Mn(II) to Mn(IV) occurs under oxygen-limiting conditions. Biological re-oxidation of Fe(II) to Fe(III) is obtained with nitrate under anaerobic conditions. Both bio-regenerated Mn(IV)-oxides and Fe(III)-hydroxides are amorphous. The pharmaceutical removal is insignificant by Mn(II)- or Fe(II)-oxidizing bacteria during regeneration. Finally, pharmaceutical removal is investigated with various Mn(IV) and Fe(III) sources. Anaerobic abiotic removal using Mn(IV) produced from drinking water treatment plants results in 23% metoprolol and 44% propranolol removal, similar to chemically synthesized Mn(IV). In contrast, Fe(III) from drinking water treatment plants outperformed chemically or biologically synthesized Fe(III); Fe (III) from drinking water treatment can remove 31-43% of propranolol via anaerobic abiotic process. In addition, one of the Fe(III)-based sorbents tested, FerroSorp ® RW, can also remove propranolol (20-25%). Biological regeneration of Mn(IV) and Fe(III) from the reduced species Mn(II) and Fe(II) could be more effective in terms of cost and treatment efficiency. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Kineococcus radiotolerans Dps forms a heteronuclear Mn-Fe ferroxidase center that may explain the Mn-dependent protection against oxidative stress.

PubMed

Ardini, Matteo; Fiorillo, Annarita; Fittipaldi, Maria; Stefanini, Simonetta; Gatteschi, Dante; Ilari, Andrea; Chiancone, Emilia

2013-06-01

The ferroxidase center of DNA-binding protein from starved cells (Dps) is a major player in the iron oxidation/detoxification process that leads to a decreased reactive oxygen species production. The possible Mn(II) participation in this process has been studied in Dps from Kineococcus radiotolerans, a radiation-resistant bacterium with a high cytosolic Mn/Fe ratio and a high capacity to survive ionizing and stress conditions. The X-ray structure of recombinant K. radiotolerans Dps loaded with Mn(II) has been solved at 2.0Å resolution. Mn(II) binding to K. radiotolerans Dps and its effect on Fe(II) oxidation have been characterized in spectroscopic measurements. In K. radiotolerans Dps, the Fe-Fe ferroxidase center can have a Mn-Fe composition. Mn(II) binds only at the high affinity, so-called A site, whereas Fe(II) binds also at the low affinity, so-called B site. The Mn-Fe and Fe-Fe centers behave distinctly upon iron oxidation by O2. A site-bound Mn(II) or Fe(II) plays a catalytic role, while B site-bound Fe(II) behaves like a substrate and can be replaced by another Fe(II) after oxidation. When H2O2 is the Fe(II) oxidant, single electrons are transferred to aromatic residues near the ferroxidase center and give rise to intra-protein radicals thereby limiting OH release in solution. The presence of the Mn-Fe center results in significant differences in the development of such intra-protein radicals. Mn(II) bound at the Dps ferroxidase center A site undergoes redox cycling provided the B site contains Fe. The results provide a likely molecular mechanism for the protective role of Mn(II) under oxidative stress conditions as it participates in redox cycling in the hetero-binuclear ferroxidase center. Copyright © 2013 Elsevier B.V. All rights reserved.

Formation of the Fe-Containing Intermetallic Compounds during Solidification of Al-5Mg-2Si-0.7Mn-1.1Fe Alloy

NASA Astrophysics Data System (ADS)

Que, Zhongping; Wang, Yun; Fan, Zhongyun

2018-06-01

Iron (Fe) is the most common and the most detrimental impurity element in Al alloys due to the formation of Fe-containing intermetallic compounds (IMCs), which are harmful to mechanical performance of the Al-alloy components. In this paper we investigate the formation of Fe-containing IMCs during solidification of an Al-5Mg-2Si-0.7Mn-1.1Fe alloy under varied solidification conditions. We found that the primary Fe-containing intermetallic compound (P-IMC) in the alloy is the BCC α-Al15(Fe,Mn)3Si2 phase and has a polyhedral morphology with {1 1 0} surface termination. The formation of the P-IMCs can be easily suppressed by increasing the melt superheat and/or cooling rate, suggesting that the nucleation of the α-Al15(Fe,Mn)3Si2 phase is difficult. In addition, we found that the IMCs with a Chinese script morphology is initiated on the {1 0 0} surfaces of the P-IMCs during the binary eutectic reaction with the α-Al phase. Both the binary and ternary eutectic IMCs are also identified as the BCC α-Al15(Fe,Mn)3Si2 phase. Furthermore, we found that the Fe content increases and the Mn content decreases in the Fe-containing intermetallic compounds with the decrease of the formation temperature, although the sum of the Fe and Mn contents in all of the IMCs is constant.

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

PubMed Central

Lovley, D R

1991-01-01

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process. PMID:1886521

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Reactive iron and manganese in estuarine sediments of the Baltic Sea: Impacts of flocculation and redox shuttling

NASA Astrophysics Data System (ADS)

Jilbert, Tom; Tiihonen, Rosa; Myllykangas, Jukka-Pekka; Asmala, Eero; Hietanen, Susanna

2016-04-01

Iron (Fe) and manganese (Mn) play important roles in sedimentary carbon cycling in both freshwater and marine systems. Dissimilatory reduction of Fe and Mn oxides is known to be a major pathway of suboxic organic matter remineralization in surface sediments, while recent studies have shown that Fe and Mn oxides may be involved in the anaerobic oxidation of methane deeper in the sediment column (e.g., Egger et al., 2015). Estuaries are transitional environments, characterized by gradients of salinity and redox conditions which impact on the mobility of Fe and Mn. In turn, the distribution of Fe and Mn in estuarine sediments, and the role of the two metals in carbon cycling, is expected to be spatially heterogeneous. However, few studies have attempted to describe the sedimentary distribution of Fe and Mn in the context of processes occurring in the estuarine water column. In particular, salinity-driven flocculation and redox shuttling are two key processes whose relative impacts on sedimentary Fe and Mn have not been clearly demonstrated. In this study we investigated the coupled water column and sedimentary cycling of Fe and Mn along a 60km non-tidal estuarine transect in the Gulf of Finland, Baltic Sea. We show that riverine Fe entering the estuary as colloidal oxides associated with dissolved organic matter (DOM) is quickly flocculated and sedimented within 5 km of the river mouth, despite the shallow lateral salinity gradient. Sediments within this range are enriched in Fe (up to twice the regional average), principally in the form of crystalline Fe oxides as determined by sequential extractions. The high crystallinity implies relative maturity of the oxide mineralogy, likely due to sustained oxic conditions and long residence time in the river catchment. Despite the reducing conditions below the sediment-water interface, Fe is largely retained in the sediments close to the river mouth. In contrast, sedimentary Mn concentrations are highest in a deep silled basin more than 10km downstream. Throughout the estuary, Mn oxides are reductively dissolved shallower in the sediment column than Fe oxides, resulting in strong effluxes of dissolved Mn from the sediments. Subsequent oxidation of bottom water dissolved Mn to particulate oxides and lateral transport ("redox shuttling") account for the sedimentary Mn enrichments in the deep silled basin. Porewater data suggest that the heterogeneity of Fe and Mn availability in the estuarine sediments may influence the relative importance of the two metals for anaerobic oxidation of methane. Egger, M. et al., Environmental Science and Technology 49(1), 277-283, 2015.

Microbial reduction of manganese oxides - Interactions with iron and sulfur

NASA Technical Reports Server (NTRS)

Myers, Charles R.; Nealson, Kenneth H.

1988-01-01

Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

USGS Publications Warehouse

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Effects of alloying elements (Mn, Co, Al, W, Sn, B, C and S) on biodegradability and in vitro biocompatibility of pure iron.

PubMed

Liu, B; Zheng, Y F

2011-03-01

Pure iron was determined to be a valid candidate material for biodegradable metallic stents in recent animal tests; however, a much faster degradation rate in physiological environments was desired. C, Mn, Si, P, S, B, Cr, Ni, Pb, Mo, Al, Ti, Cu, Co, V and W are common alloying elements in industrial steels, with Cr, Ni, Mo, Cu, Ti, V and Si being acknowledged as beneficial in enhancing the corrosion resistance of iron. The purpose of the present work (using Fe-X binary alloy models) is to explore the effect of the remaining alloying elements (Mn, Co, Al, W, B, C and S) and one detrimental impurity element Sn on the biodegradability and biocompatibility of pure iron by scanning electron microscopy, X-ray diffraction, metallographic observation, tensile testing, microhardness testing, electrochemical testing, static (for 6 months) and dynamic (for 1 month with various dissolved oxygen concentrations) immersion testing, cytotoxicity testing, hemolysis and platelet adhesion testing. The results showed that the addition of all alloying elements except for Sn improved the mechanical properties of iron after rolling. Localized corrosion of Fe-X binary alloys was observed in both static and dynamic immersion tests. Except for the Fe-Mn alloy, which showed a significant decrease in corrosion rate, the other Fe-X binary alloy corrosion rates were close to that of pure iron. It was found that compared with pure iron all Fe-X binary alloys decreased the viability of the L929 cell line, none of experimental alloying elements significantly reduced the viability of vascular smooth muscle cells and all the elements except for Mn increased the viability of the ECV304 cell line. The hemolysis percentage of all Fe-X binary alloy models were less than 5%, and no sign of thrombogenicity was observed. In vitro corrosion and the biological behavior of these Fe-X binary alloys are discussed and a corresponding mechanism of corrosion of Fe-X binary alloys in Hank's solution proposed. As a concluding remark, Co, W, C and S are recommended as alloying elements for biodegradable iron-based biomaterials. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Iron and Arsenic Speciation During As(III) Oxidation by Manganese Oxides in the Presence of Fe(II): Molecular-Level Characterization Using XAFS, Mössbauer, and TEM Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Kukkadapu, Ravi K.; Livi, Kenneth J. T.

The redox state and speciation of metalloid arsenic (As) determine its toxicity and mobility. Knowledge of biogeochemical processes influencing the As redox state is therefore important to understand and predict its environmental behavior. Many previous studies examined As(III) oxidation by various Mn-oxides, but little is known the environmental influences (e.g. co-existing ions) on such process. In this study, we investigated the mechanisms of As(III) oxidation by a poorly crystalline hexagonal birnessite (δ-MnO2) in the presence of Fe(II) using X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS). As K-edge X-ray absorption nearmore » edge spectroscopy (XANES) analysis revealed that, at low Fe(II) concentration (100 μM), As(V) was the predominant As species on the solid phase, while at higher Fe(II) concentration (200-1000 μM), both As(III) and As(V) were sorbed on the solid phase. As K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) analysis showed an increasing As-Mn/Fe distance over time, indicating As prefers to bind with the newly formed Fe(III)-(hydr)oxides. As adsorbed on Fe(III)-(hydr)oxides as a bidentate binuclear corner-sharing complex. Both Mössbauer and TEM-EDS investigations demonstrated that the oxidized Fe(III) products formed during Fe(II) oxidation by δ-MnO2 were predominantly ferrihydrite, goethite, and ferric arsenate like compounds. However, Fe EXAFS analysis also suggested the formation of a small amount of lepidocrocite. The Mn K-edge XANES data indicated that As(III) and Fe(II) oxidation occurs as a two electron transfer with δ-MnO2 and the observed Mn(III) is due to conproportionation of surface sorbed Mn(II) with Mn(IV) in δ-MnO2 structure. This study reveals that the mechanisms of As(III) oxidation by δ-MnO2 in the presence of Fe(II) are very complex, involving many simultaneous reactions, and the formation of Fe(III)-(hydr)oxides plays a very important role in reducing As mobility.« less

Magnetic susceptibilities of liquid Cr-Au, Mn-Au and Fe-Au alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohno, S.; Shimakura, H.; Tahara, S.

The magnetic susceptibility of liquid Cr-Au, Mn-Au, Fe-Au and Cu-Au alloys was investigated as a function of temperature and composition. Liquid Cr{sub 1-c}Au{sub c} with 0.5 ≤ c and Mn{sub 1-c}Au{sub c} with 0.3≤c obeyed the Curie-Weiss law with regard to their dependence of χ on temperature. The magnetic susceptibilities of liquid Fe-Au alloys also exhibited Curie-Weiss behavior with a reasonable value for the effective number of Bohr magneton. On the Au-rich side, the composition dependence of χ for liquid TM-Au (TM=Cr, Mn, Fe) alloys increased rapidly with increasing TM content, respectively. Additionally, the composition dependences of χ for liquidmore » Cr-Au, Mn-Au, and Fe-Au alloys had maxima at compositions of 50 at% Cr, 70 at% Mn, and 85 at% Fe, respectively. We compared the composition dependences of χ{sub 3d} due to 3d electrons for liquid binary TM-M (M=Au, Al, Si, Sb), and investigated the relationship between χ{sub 3d} and E{sub F} in liquid binary TM-M alloys at a composition of 50 at% TM.« less

The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-01

In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Elemental Mercury Oxidation over Fe-Ti-Mn Spinel: Performance, Mechanism, and Reaction Kinetics.

PubMed

Xiong, Shangchao; Xiao, Xin; Huang, Nan; Dang, Hao; Liao, Yong; Zou, Sijie; Yang, Shijian

2017-01-03

The design of a high-performance catalyst for Hg 0 oxidation and predicting the extent of Hg 0 oxidation are both extremely limited due to the uncertainties of the reaction mechanism and the reaction kinetics. In this work, Fe-Ti-Mn spinel was developed as a high-performance catalyst for Hg 0 oxidation, and the reaction mechanism and the reaction kinetics of Hg 0 oxidation over Fe-Ti-Mn spinel were studied. The reaction orders of Hg 0 oxidation over Fe-Ti-Mn spinel with respect to gaseous Hg 0 concentration and gaseous HCl concentration were approximately 1 and 0, respectively. Therefore, Hg 0 oxidation over Fe-Ti-Mn spinel mainly followed the Eley-Rideal mechanism (i.e., the reaction of gaseous Hg 0 with adsorbed HCl), and the rate of Hg 0 oxidation mainly depended on Cl • concentration on the surface. As H 2 O, SO 2 , and NO not only inhibited Cl • formation on the surface but also interfered with the interface reaction between gaseous Hg 0 and Cl • on the surface, Hg 0 oxidation over Fe-Ti-Mn spinel was obviously inhibited in the presence of H 2 O, SO 2 , and NO. Furthermore, the extent of Hg 0 oxidation over Fe-Ti-Mn spinel can be predicted according to the kinetic parameter k E-R , and the predicted result was consistent with the experimental result.

As(III) oxidation by MnO2 during groundwater treatment.

PubMed

Gude, J C J; Rietveld, L C; van Halem, D

2017-03-15

The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO 2 ), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO 2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO 2 powder was a very pure - commercially available - natural MnO 2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO 2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO 2 surface (at pH 7). Therefore it is concluded that just because MnO 2 is present in a filter bed, it does not necessarily mean that MnO 2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO 2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

NASA Astrophysics Data System (ADS)

Swaminathan, Srinivasan; Krishna, Nanda Gopala; Kim, Dong-Ik

2015-10-01

Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr2O4 and MnCr2O4 along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

Effect of Iron(II) on Arsenic Sequestration by δ-MnO 2 : Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yun; Li, Wei; Sparks, Donald L.

2015-10-18

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO 2) in the presence of Fe(II)more » prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO 4 3–) and calcium (Ca 2+). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.« less

Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-17

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

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.

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.

Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

NASA Astrophysics Data System (ADS)

Cavazos, A. R.; Taillefert, M.; Glass, J. B.

2016-12-01

The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

Concretionary manganese-iron oxides in streams and their usefulness as a sample medium for geochemical prospecting

USGS Publications Warehouse

Nowlan, G.A.

1976-01-01

Correlation studies of 400 samples of sieved stream sediments and 325 samples of fluvial, concretionary Mn-Fe oxides from Maine resulted in the separation of elements into the following categories: (1) elements not scavenged by Mn-Fe oxides - B, Cr, K, Mg, Rb, Sc, Ti, V, and Zr; (2) elements probably not scavenged by Mn-Fe oxides - Ag, Be, Ca, Ga, La, Sb, and Y; (3) elements scavenged weakly by Mn-Fe oxides - Cu, Mo, Pb, and Sr; (4) elements scavenged strongly by Mn oxides - Ba, Cd, Co, Ni, Tl, and Zn; and (5) elements scavenged strongly by Fe oxides - As and In. Studies of the scavenged elements showed that the deviation from the mean is characteristically greater in oxide samples as compared to sieved sediments from the same locality. However, a significant increase in contrast between anomalous and background localities, when oxides are the sample medium, more than offsets the disadvantage of data scatter. The use of oxides as a sampling medium clearly and significantly accentuates anomalous localities. In general, non-ratioed data on oxides give very nearly the same results as data consisting of scavenged elements ratioed to Mn and Fe. However, ratioed data expand the geographic area of specific anomalies. Cd and Zn consistently show strong correlations with concretionary Mn-Fe oxides, but their concentrations in the oxides do not generally show as much contrast between anomalous and background localities as do Cu, Mo, and Pb. These latter elements are strongly scavenged where rocks are mineralized. ?? 1976.

Positron Annihilation Spectroscopy Characterization of Nanostructural Features in Reactor Steels

NASA Astrophysics Data System (ADS)

Glade, Stephen; Wirth, Brian; Asoka-Kumar, Palakkal; Sterne, Philip; Alinger, Matthew; Odette, George

2004-03-01

Irradiation embrittlement in nuclear reactor pressure vessel steels results from the formation of a high number density of nanometer sized copper rich precipitates and sub-nanometer defect-solute clusters. We present results of study to characterize the size and compositions of simple binary and ternary Fe-Cu-Mn model alloys and more representative Fe-Cu-Mn-Ni-Si-Mo-C reactor pressure vessel steels using positron annihilation spectroscopy (PAS). Using a recently developed spin-polarized PAS technique, we have also measured the magnetic properties of the nanometer-sized copper rich precipitates. Mn retards the precipitation kinetics and inhibits large vacancy cluster formation, suggesting a strong Mn-vacancy interaction which reduces radiation enhanced diffusion. The spin-polarized PAS measurements reveal the non-magnetic nature of the copper precipitates, discounting the notion that the precipitates contain significant quantities of Fe and providing an upper limit of at most a few percent Fe in the precipitates. PAS results on oxide dispersion-strengthened steel for use in fusion reactors will also be presented. Part of this work was performed under the auspices of the US Department of Energy by the University of California, Lawrence Livermore National Laboratory, under contract No. W-7405-ENG-48 with partial support provided from Basic Energy Sciences, Division of Materials Science.

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.

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

PubMed

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

Sorption of Ferric Iron from Ferrioxamine B to Synthetic and Biogenic Layer Type Manganese Oxides

NASA Astrophysics Data System (ADS)

Duckworth, O.; John, B.; Sposito, G.

2006-12-01

Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effects of predominantly Mn(IV) oxides, we studied the sorption reaction of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(III, IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over at pH 8. After 72 hours equilibration time, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the EXAFS spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to into the mineral structure at multiple sites with no evidence of DFOB complexation, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron in marine and terrestrial environments.

Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

1989-01-01

The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

Synthesis of α-Fe2O3 and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates

PubMed Central

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Sort, Jordi

2018-01-01

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N2 atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe2O3) foams are obtained from the metallic iron slurry independently of the N2 flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N2 flow. While the main phases for a N2 flow rate of 180 L/h are α-Fe2O3 and FeMnO3, the predominant phase for high N2 flow rates (e.g., 650 L/h) is Fe2MnO4. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe2MnO4 foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N2 flow rate (i.e., the amount of Fe2MnO4) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids. PMID:29439450

Study of manganese binding to the ferroxidase centre of human H-type ferritin.

PubMed

Ardini, Matteo; Howes, Barry D; Fiorillo, Annarita; Falvo, Elisabetta; Sottini, Silvia; Rovai, Donella; Lantieri, Marco; Ilari, Andrea; Gatteschi, Dante; Spina, Gabriele; Chiancone, Emilia; Stefanini, Simonetta; Fittipaldi, Maria

2018-05-01

Ferritins are ubiquitous and conserved proteins endowed with enzymatic ferroxidase activity, that oxidize Fe(II) ions at the dimetal ferroxidase centre to form a mineralized Fe(III) oxide core deposited within the apo-protein shell. Herein, the in vitro formation of a heterodimetal cofactor constituted by Fe and Mn ions has been investigated in human H ferritin (hHFt). Namely, Mn and Fe binding at the hHFt ferroxidase centre and its effects on Fe(II) oxidation have been investigated by UV-Vis ferroxidation kinetics, fluorimetric titrations, multifrequency EPR, and preliminary Mössbauer spectroscopy. Our results show that in hHFt, both Fe(II) and Mn(II) bind the ferroxidase centre forming a Fe-Mn cofactor. Moreover, molecular oxygen seems to favour Mn(II) binding and increases the ferroxidation activity of the Mn-loaded protein. The data suggest that Mn influences the Fe binding and the efficiency of the ferroxidation reaction. The higher efficiency of the Mn-Fe heterometallic centre may have a physiological relevance in specific cell types (i.e. glia cells), where the concentration of Mn is the same order of magnitude as iron. Copyright © 2018 Elsevier Inc. All rights reserved.

Sorption of Ferrioxime B to Synthetic and Biogenic layer type Mn Oxides

NASA Astrophysics Data System (ADS)

Duckworth, O. W.; Bargar, J. R.; Sposito, G.

2005-12-01

Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effect of solid-phase Mn(IV), we studied the sorption reaction of ferrioxamine B [principally the species, Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore, desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over the pH range between 5 and 9. After 72 h equilibration time at pH 8, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-Ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the X-ray absorption spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed with DFOB, but instead is incorporated into the mineral structure, thus implying that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron.

Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

PubMed

Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

2016-12-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb. Copyright © 2016 Elsevier Ltd. All rights reserved.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

NASA Astrophysics Data System (ADS)

Postma, D.; Appelo, C. A. J.

2000-04-01

The reduction of Mn-oxide by Fe2+ was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement of adsorbed Ca2+ with Mg2+. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the FeCl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe2+ reacts with MnO2 producing Fe(OH)3, Mn2+ and H+. The protons are transported downstream and cause the disproportionation of MnOOH at a separate reaction front. Between the two Mn reaction fronts, the dissolution and precipitation of Fe(OH)3 and Al(OH)3 act as proton buffers. Reactive transport modeling, using the code PHREEQC 2.0, was done to quantify and analyze the reaction controls and the coupling between transport and chemical processes. A model containing only mineral equilibria constraints for birnessite, manganite, gibbsite, and ferrihydrite, was able to explain the overall reaction pattern with the sequential appearance of Mn2+, Al3+, Fe3+, and Fe2+ in the column outlet solution. However, the initial breakthrough of a peak of Ca2+ and the observed pH buffering indicated that exchange processes were of importance as well. The amount of potential exchangers, such as birnessite and ferrihydrite, did vary in the course of the experiment. A model containing surface complexation coupled to varying concentrations of birnessite and ferrihydrite and a constant charge exchanger in addition to mineral equilibria provided a satisfactory description of the distribution of all solutes in time and space. However, the observed concentration profiles are more gradual than indicated by the equilibrium model. Reaction kinetics for the dissolution of MnO2 and MnOOH and dissolution of Al(OH)3 were incorporated in the model, which explained the shape of the breakthrough curves satisfactorily. The results of this study emphasize the importance of understanding the interplay between chemical reactions and transport in addition to interactions between redox, proton buffering, and adsorption processes when dealing with natural sediments. Reactive transport modeling is a powerful tool to analyze and quantify such interactions.

Mechanism of selenite removal by a mixed adsorbent based on Fe-Mn hydrous oxides studied using X-ray absorption spectroscopy.

PubMed

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.

Secondary Fe- and Mn-Oxides Associated with Faults Near Moab, Utah: Records of Past Fluid Flow

NASA Astrophysics Data System (ADS)

Garcia, V. H.; Reiners, P. W.

2015-12-01

Secondary Fe- and Mn-oxides are locally common near faults and fractures, and as cements within sandstones of the Colorado Plateau, and provide evidence of past fluid-flow. Here we describe textural, mineralogic, and geochronologic observations from fault-zone Fe- and Mn-oxide mineralization in Flat Iron Mesa, near Moab, Utah. Several hypotheses have been proposed for their origin, including reactions associated with the mixing of deep reduced and near-surface oxygenated waters. We integrate field observations, detailed SEM and petrographic observations, geochemical models, (U-Th)/He and Ar/Ar dating, and other data to develop interpretations of the formation of these deposits. SEM imaging shows that sandstone matrix cement adjacent to the faults follows two precipitation sequences: Fe-oxide followed by barite and Fe-oxide followed by Mn-oxide. Dense oxide layers also accumulated in cm-scale fractures near faults, and show the following precipitation sequence: Fe-oxide, barite, Ba rich Mn-oxide, and pure Mn-oxide. The latter sequence is observed at larger scale across faults in one site in Flat Iron Mesa. Our new He dates for Mn-oxides are 1.7-2.9 Ma while Fe-oxide dates are 2.7-3.0 Ma. If these dates represent formation ages, they are consistent with the interpreted precipitation sequence but would require protracted mineralization over Ma-timescales. Alternatively, they may represent varying degrees of He retentivity in earlier formed deposits. Previous Ar/Ar dates have been interpreted as a 20-25 Ma formation age. Ongoing Ar/Ar and He diffusion studies will resolve this discordance. Assuming the previous Ar dates do not reflect contamination by detrital K-bearing phases and do reflect oxide formation, potential interpretations for the younger He ages include recent U-Th addition, recrystallization, later oxide growth, or large diffusive He loss at low temperatures.

Magnetically retrievable nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) spinel nanocatalyst for alcohol oxidation

NASA Astrophysics Data System (ADS)

Bhat, Pooja B.; Bhat, Badekai Ramachandra

2016-03-01

Ultrasmall nickel hydroxide functionalised AFe2O4 (A = Mn, Ni) nanocatalyst was synthesized by traditional co-precipitation method and was examined for oxidation of aromatic alcohols to carbonyls using hydrogen peroxide as terminal oxidant. A very high surface area of 104.55 m2 g-1 was achieved for ferromagnetic MnFe2O4 and 100.50 m2 g-1 for superparamagnetic NiFe2O4, respectively. Efficient oxidation was observed due to the synergized effect of nickel hydroxide (bronsted base) on Lewis center (Fe) of the nanocatalyst. Catalyst recycling experiments revealed that the ultrasmall nanocatalyst can be easily recovered by external magnet and applied for nearly complete oxidation of alcohols for at least five successive cycles. Furthermore, the nickel hydroxide functionalised ultrasmall nanocatalyst exhibited higher efficiency for benzyl alcohol oxidation compared to Ni(OH)2, bare MnFe2O4 and NiFe2O4. Higher conversion rate was observed for nickel hydroxide functionalised NiFe2O4 compared to MnFe2O4. Ultrasmall magnetic nickel hydroxide functionalised nanocatalyst showed environmental friendly, greener route for the oxidation of alcohols without significant loss in activity and selectivity within successive runs.

Evidence That the [beta] Subunit of Chlamydia trachomatis Ribonucleotide Reductase Is Active with the Manganese Ion of Its Manganese(IV)/Iron(III) Cofactor in Site 1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dassama, Laura M.K.; Boal, Amie K.; Krebs, Carsten

2014-10-02

The reaction of a class I ribonucleotide reductase (RNR) begins when a cofactor in the {beta} subunit oxidizes a cysteine residue {approx}35 {angstrom} away in the {alpha} subunit, generating a thiyl radical. In the class Ic enzyme from Chlamydia trachomatis (Ct), the cysteine oxidant is the Mn{sup IV} ion of a Mn{sup IV}/Fe{sup III} cluster, which assembles in a reaction between O{sub 2} and the Mn{sup II}/Fe{sup II} complex of {beta}. The heterodinuclear nature of the cofactor raises the question of which site, 1 or 2, contains the Mn{sup IV} ion. Because site 1 is closer to the conserved locationmore » of the cysteine-oxidizing tyrosyl radical of class Ia and Ib RNRs, we suggested that the Mn{sup IV} ion most likely resides in this site (i.e., {sup 1}Mn{sup IV}/{sup 2}Fe{sup III}), but a subsequent computational study favored its occupation of site 2 ({sup 1}Fe{sup III}/{sup 2}Mn{sup IV}). In this work, we have sought to resolve the location of the Mn{sup IV} ion in Ct RNR-{beta} by correlating X-ray crystallographic anomalous scattering intensities with catalytic activity for samples of the protein reconstituted in vitro by two different procedures. In samples containing primarily Mn{sup IV}/Fe{sup III} clusters, Mn preferentially occupies site 1, but some anomalous scattering from site 2 is observed, implying that both {sup 1}Mn{sup II}/{sup 2}Fe{sup II} and {sup 1}Fe{sup II}/{sup 2}Mn{sup II} complexes are competent to react with O{sub 2} to produce the corresponding oxidized states. However, with diminished Mn{sup II} loading in the reconstitution, there is no evidence for Mn occupancy of site 2, and the greater activity of these 'low-Mn' samples on a per-Mn basis implies that the {sup 1}Mn{sup IV}/{sup 2}Fe{sup III}-{beta} is at least the more active of the two oxidized forms and may be the only active form.« less

ROLE OF IRON AND MANGANESE OXIDES IN BIOSOLIDS AND BIOSOLIDS-AMENDED SOILS ON METAL BINDING

EPA Science Inventory

Biosolids contain high levels of Fe, Mn, and Al. Surfaces of freshly precipitated metal oxides, especially Fe and Mn, are known to be highly active sites for most dissolved metal ion species. We nw have metal sorption/desorption data that illustrate the importance of Fe and Mn fr...

Fractionation and risk assessment of Fe and Mn in surface sediments from coastal sites of Sonora, Mexico (Gulf of California).

PubMed

Jara-Marini, Martín E; García-Camarena, Raúl; Gómez-Álvarez, Agustín; García-Rico, Leticia

2015-07-01

The aim of this study was to evaluate Fe and Mn distribution in geochemical fractions of the surface sediment of four oyster culture sites in the Sonora coast, Mexico. A selective fractionation scheme to obtain five fractions was adapted for the microwave system. Surface sediments were analyzed for carbonates, organic matter contents, and Fe and Mn in geochemical fractions. The bulk concentrations of Fe ranged from 10,506 to 21,918 mg/kg (dry weight, dry wt), and the bulk concentrations of Mn ranged from 185.1 to 315.9 mg/kg (dry wt) in sediments, which was low and considered as non-polluted in all of the sites. The fractionation study indicated that the major geochemical phases for the metals were the residual, as well as the Fe and Mn oxide fractions. The concentrations of metals in the geochemical fractions had the following order: residual > Fe and Mn oxides > organic matter > carbonates > interchangeable. Most of the Fe and Mn were linked to the residual fraction. Among non-residual fractions, high percentages of Fe and Mn were linked to Fe and Mn oxides. The enrichment factors (EFs) for the two metals were similar in the four studied coasts, and the levels of Fe and Mn are interpreted as non-enrichment (EF < 1) because the metals concentrations were within the baseline concentrations. According to the environmental risk assessment codes, Fe and Mn posed no risk and low risk, respectively. Although the concentrations of Fe and Mn were linked to the residual fraction, the levels in non-residual fractions may significantly result in the transference of other metals, depending on several physico-chemical and biological factors.

Characterization of iron and manganese minerals and their associated microbiota in different mine sites to reveal the potential interactions of microbiota with mineral formation.

PubMed

Park, Jin Hee; Kim, Bong-Soo; Chon, Chul-Min

2018-01-01

Different environmental conditions such as pH and dissolved elements of mine stream induce precipitation of different minerals and their associated microbial community may vary. Therefore, mine precipitates from various environmental conditions were collected and their associated microbiota were analyzed through metagenomic DNA sequencing. Various Fe and Mn minerals including ferrihydrite, schwertmannite, goethite, birnessite, and Mn-substituted δ-FeOOH (δ-(Fe 1-x , Mn x )OOH) were found in the different environmental conditions. The Fe and Mn minerals were enriched with toxic metal(loid)s including As, Cd, Ni and Zn, indicating they can act as scavengers of toxic metal(loid)s in mine streams. Under acidic conditions, Acidobacteria was dominant phylum and Gallionella (Fe oxidizing bacteria) was the predominant genus in these Fe rich environments. Manganese oxidizing bacteria, Hyphomicrobium, was found in birnessite forming environments. Leptolyngbya within Cyanobacteria was found in Fe and Mn oxidizing environments, and might contribute to Fe and Mn oxidation through the production of molecular oxygen. The potential interaction of microbial community with minerals in mine sites can be traced by analysis of microbial community in different Fe and Mn mineral forming environments. Iron and Mn minerals contribute to the removal of toxic metal(loid)s from mine water. Therefore, the understanding characteristics of mine precipitates and their associated microbes helps to develop strategies for the management of contaminated mine water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier.

PubMed

Wang, Baowen; Gao, Chuchang; Wang, Weishu; Zhao, Haibo; Zheng, Chuguang

2014-05-01

Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier (OC) was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi (LZ) bituminous coal, was performed in a thermogravimetric analyzer (TGA)-Fourier transform infrared (FT-IR) spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFe2O4 OC was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn3O4 or Fe2O3, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe3O4 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Manganese oxide shuttling in pre-GOE oceans - evidence from molybdenum and iron isotopes

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Gantert, Niklas; Beukes, Nicolas J.; Schoenberg, Ronny

2016-10-01

The local occurrence of oxygen-rich shallow marine water environments has been suggested to significantly predate atmospheric oxygenation, which occurred during the Great Oxidation Event (GOE) ca. 2.4 billion years ago. However, the potential influence of such 'oxygen oases' on the mobility, distribution and isotopic composition of redox sensitive elements remains poorly understood. Here, we provide new molybdenum and iron isotopic data from shallow marine carbonate and silicate iron formations of the Koegas Subgroup, South Africa, that confirm local ocean redox stratification prior to the GOE. Mn concentrations correlate negatively with both δ98 Mo and δ56 Fe values, which highlights the substantial role of particulate manganese for the cycling of Mo and Fe in the Paleoproterozoic oceans. Based on these trends we propose that pore water molybdate was recharged (1) by the diffusional transport of seawater molybdate with high δ98 Mo and (2) by the re-liberation of adsorbed molybdate with low δ98 Mo during Mn oxide dissolution within the sediment. The relative contribution of isotopically light Mo is highest close to a Mn chemocline, where the flux of Mn oxides is largest, causing the negative correlation of Mn concentrations and δ98 Mo values in the Koegas sediments. The negative correlation between δ56 Fe values and Mn concentrations is likely related to Fe isotope fractionation during Fe(II) oxidation by Mn oxides, resulting in lower δ56 Fe values in the uppermost water column close to a Mn chemocline. We argue that the preservation of these signals within Paleoproterozoic sediments implies the existence of vertically extended chemoclines with a smoother gradient, probably as a result of low atmospheric oxygen concentrations. Furthermore, we suggest that abiotic oxidation of Fe(II) by a Mn oxide particle shuttle might have promoted the deposition of the Koegas iron formations.

Molybdenum isotopes in modern marine hydrothermal Fe/Mn deposits: Implications for Archean and Paleoproterozoic Mo cycles

NASA Astrophysics Data System (ADS)

Goto, K. T.; Hein, J. R.; Shimoda, G.; Aoki, S.; Ishikawa, A.; Suzuki, K.; Gordon, G. W.; Anbar, A. D.

2016-12-01

Molybdenum isotope (δ98/95Mo) variations recorded in Archean and Paleoproterozoic Fe/Mn-rich sediments have been used to constrain ocean redox conditions at the time of deposition (Canfield et al., 2013 PNAS; Planavsky et al., 2014 Nat. Geo.; Kurzweil et al., 2015 GCA). However, except for hydrogenous Fe-Mn crusts (Siebert et al., 2003), δ98/95Mo variation of modern Fe and Mn oxide deposits has been poorly investigated. Marine hydrothermal systems are thought to be the major source of Fe and Mn in Archean and Paleoproterozoic Fe- and Mn-rich sediments. Hence, to accurately interpret Mo isotope data of those ancient sedimentary rocks, it is important to evaluate the possible influence of hydrothermally derived Mo on δ98/95Mo of modern Fe- and Mn-rich sediments. In this study, we analyzed Mo isotopic compositions of one hydrothermal Fe oxide and 15 Mn oxides from five different hydrothermal systems in the modern ocean. The Fe oxide is composed mainly of goethite, and has a δ98/95Mo of 0.7‰, which is 1.4‰ lighter than that of present-day seawater. The observed offset is similar to isotope fractionation observed during adsorption experiments of Mo on goethite (Δ98/95Mogoethite-solution = -1.4 ± 0.5%; Goldberg et al., 2009 GCA). The 15 hydrothermal Mn oxides show large variations in δ98/95Mo ranging from -1.7 to 0.5‰. However, most of the values are similar to those of modern hydrogenous Fe-Mn crusts (Siebert et al., 2003 EPSL), and fall within the range of estimated δ98/95Mo of Mn oxides precipitated from present-day seawater using the isotope offset reported from adsorption experiments (Δ98/95Mo = -2.7 ± 0.3‰; Wasylenki et al., 2008 GCA). These findings indicate that seawater is the dominant source of Mo for modern hydrothermal Fe and Mn deposits. However, the observed large variation indicates that the contribution Mo from local hydrothermal systems is not negligible. The oceanic Mo inventory during the Archean and Paleoproterozoic is thought to be much smaller than that of present-day (Scott et al., 2008 Nature). Hence, δ98/95Mo of Archean and Paleoproterozoic Fe- and Mn-rich sediments could be strongly influenced by hydrothermally derived Mo, which may contrast to modern hydrothermal deposits. Possible Archean and Paleoproterozoic Mo cycles constrained by these data will also be discussed.

Oxygen-participated electrochemistry of new lithium-rich layered oxides Li3MRuO5 (M = Mn, Fe).

PubMed

Laha, S; Natarajan, S; Gopalakrishnan, J; Morán, E; Sáez-Puche, R; Alario-Franco, M Á; Dos Santos-Garcia, A J; Pérez-Flores, J C; Kuhn, A; García-Alvarado, F

2015-02-07

We describe the synthesis, crystal structure and lithium deinsertion-insertion electrochemistry of two new lithium-rich layered oxides, Li3MRuO5 (M = Mn, Fe), related to rock salt based Li2MnO3 and LiCoO2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m) where Li and (Li0.2Mn0.4Ru0.4) layers alternate along the c-axis, while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R3[combining macron]m) structure where Li and (Li0.2Fe0.4Ru0.4) layers are stacked alternately. Magnetic measurements indicate for Li3MnRuO5 the presence of Mn(3+) and low spin configuration for Ru(4+) where the itinerant electrons occupy a π*-band. The onset of a net maximum in the χ vs. T plot at 9.5 K and the negative value of the Weiss constant (θ) of -31.4 K indicate the presence of antiferromagnetic superexchange interactions according to different pathways. Lithium electrochemistry shows a similar behaviour for both oxides and related to the typical behaviour of Li-rich layered oxides where participation of oxide ions in the electrochemical processes is usually found. A long first charge process with capacities of 240 mA h g(-1) (2.3 Li per f.u.) and 144 mA h g(-1) (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. An initial sloping region (OCV to ca. 4.1 V) is followed by a long plateau (ca. 4.3 V). Further discharge-charge cycling points to partial reversibility (ca. 160 mA h g(-1) and 45 mA h g(-1) for Mn and Fe, respectively). Nevertheless, just after a few cycles, cell failure is observed. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn(3+) and Ru(4+) are partially oxidized to Mn(4+) and Ru(5+) in the sloping region at low voltage, while in the long plateau, O(2-) is also oxidized. Oxygen release likely occurs which may be the cause for failure of cells upon cycling. Interestingly, some other Li-rich layered oxides have been reported to cycle acceptably even with the participation of the O(2-) ligand in the reversible redox processes. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O(2-) (plateau) while Fe seems to retain its 3+ state.

Critical Evaluations and Thermodynamic Optimizations of the MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 Systems

NASA Astrophysics Data System (ADS)

Kang, Youn-Bae; Jung, In-Ho

2017-06-01

A critical evaluation and thermodynamic modeling for thermodynamic properties of all oxide phases and phase diagrams in the Fe-Mn-Si-O system (MnO-Mn2O3-SiO2 and FeO-Fe2O3-MnO-Mn2O3-SiO2 systems) are presented. Optimized Gibbs energy parameters for the thermodynamic models of the oxide phases were obtained which reproduce all available and reliable experimental data within error limits from 298 K (25°C) to above the liquidus temperatures at all compositions covering from known oxide phases, and oxygen partial pressure from metal saturation to 0.21 bar. The optimized thermodynamic properties and phase diagrams are believed to be the best estimates presently available. Slag (molten oxide) was modeled using the modified quasichemical model in the pair approximation. Olivine (Fe2SiO4-Mn2SiO4) was modeled using two-sublattice model in the framework of the compound energy formalism (CEF), while rhodonite (MnSiO3-FeSiO3) and braunite (Mn7SiO_{12} with excess Mn2O3) were modeled as simple Henrian solutions. It is shown that the already developed models and databases of two spinel phases (cubic- and tetragonal-(Fe, Mn)3O4) using CEF [Kang and Jung, J. Phys. Chem. Solids (2016), vol. 98, pp. 237-246] can successfully be integrated into a larger thermodynamic database to be used in practically important higher order system such as silicate. The database of the model parameters can be used along with a software for Gibbs energy minimization in order to calculate any type of phase diagram section and thermodynamic properties.

Hybrid supercapacitor devices based on MnCo2O4 as the positive electrode and FeMn2O4 as the negative electrode

NASA Astrophysics Data System (ADS)

Nagamuthu, Sadayappan; Vijayakumar, Subbukalai; Lee, Seong-Hun; Ryu, Kwang-Sun

2016-12-01

MnCo2O4 nanosheets and FeMn2O4 nanospheres were synthesized using a hydrothermal method. Choline chloride was used as the capping agent during the preparation of the nanoparticles. XRD patterns confirmed the spinel structure of MnCo2O4 and FeMn2O4. XPS measurements were used to determine the oxidation state of the prepared spinel metal oxides. HRTEM images revealed the formation of hexagonal nanosheets of MnCo2O4 and nanospheres of FeMn2O4. Electrochemical measurements were made for both positive and negative electrodes using three electrode systems. MnCo2O4 Exhibits 282C g-1 and FeMn2O4 yields 110C g-1 at a specific current of 1 A g-1. Hybrid supercapacitor device was fabricated using MnCo2O4 as the positive and FeMn2O4 as the negative electrode material. The hybrid supercapacitor device was delivered a maximum power of 37.57 kW kg-1.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

Catalytic ozonation of petroleum refinery wastewater utilizing Mn-Fe-Cu/Al2O 3 catalyst.

PubMed

Chen, Chunmao; Yoza, Brandon A; Wang, Yandan; Wang, Ping; Li, Qing X; Guo, Shaohui; Yan, Guangxu

2015-04-01

There is of great interest to develop an economic and high-efficient catalytic ozonation system (COS) for the treatment of biologically refractory wastewaters. Applications of COS require options of commercially feasible catalysts. Experiments in the present study were designed to prepare and investigate a novel manganese-iron-copper oxide-supported alumina-assisted COS (Mn-Fe-Cu/Al2O3-COS) for the pretreatment of petroleum refinery wastewater. The highly dispersed composite metal oxides on the catalyst surface greatly promoted the performance of catalytic ozonation. Hydroxyl radical mediated oxidation is a dominant reaction in Mn-Fe-Cu/Al2O3-COS. Mn-Fe-Cu/Al2O3-COS enhanced COD removal by 32.7% compared with a single ozonation system and by 8-16% compared with Mn-Fe/Al2O3-COS, Mn-Cu/Al2O3-COS, and Fe-Cu/Al2O3-COS. The O/C and H/C ratios of oxygen-containing polar compounds significantly increased after catalytic ozonation, and the biodegradability of petroleum refinery wastewater was significantly improved. This study illustrates potential applications of Mn-Fe-Cu/Al2O3-COS for pretreatment of biologically refractory wastewaters.

Synthesis of α-Fe₂O₃ and Fe-Mn Oxide Foams with Highly Tunable Magnetic Properties by the Replication Method from Polyurethane Templates.

PubMed

Feng, Yuping; Fornell, Jordina; Zhang, Huiyan; Solsona, Pau; Barό, Maria Dolors; Suriñach, Santiago; Pellicer, Eva; Sort, Jordi

2018-02-11

Open cell foams consisting of Fe and Fe-Mn oxides are prepared from metallic Fe and Mn powder precursors by the replication method using porous polyurethane (PU) templates. First, reticulated PU templates are coated by slurry impregnation. The templates are then thermally removed at 260 °C and the debinded powders are sintered at 1000 °C under N₂ atmosphere. The morphology, structure, and magnetic properties are studied by scanning electron microscopy, X-ray diffraction and vibrating sample magnetometry, respectively. The obtained Fe and Fe-Mn oxide foams possess both high surface area and homogeneous open-cell structure. Hematite (α-Fe₂O₃) foams are obtained from the metallic iron slurry independently of the N₂ flow. In contrast, the microstructure of the FeMn-based oxide foams can be tailored by adjusting the N₂ flow. While the main phases for a N₂ flow rate of 180 L/h are α-Fe₂O₃ and FeMnO₃, the predominant phase for high N₂ flow rates (e.g., 650 L/h) is Fe₂MnO₄. Accordingly, a linear magnetization versus field behavior is observed for the hematite foams, while clear hysteresis loops are obtained for the Fe₂MnO₄ foams. Actually, the saturation magnetization of the foams containing Mn increases from 5 emu/g to 52 emu/g when the N₂ flow rate (i.e., the amount of Fe₂MnO₄) is increased. The obtained foams are appealing for a wide range of applications, such as electromagnetic absorbers, catalysts supports, thermal and acoustic insulation systems or wirelessly magnetically-guided porous objects in fluids.

Reduced arsenic accumulation in indica rice (Oryza sativa L.) cultivar with ferromanganese oxide impregnated biochar composites amendments.

PubMed

Lin, Lina; Gao, Minling; Qiu, Weiwen; Wang, Di; Huang, Qing; Song, Zhengguo

2017-12-01

The effects of biochar (BC) and ferromanganese oxide biochar composites (FMBC 1 and FMBC 2 ) on As (Arsenic) accumulation in rice were determined using a pot experiment. Treatments with BC or FMBC improved the dry weights of rice roots, stems, leaves, and grains in soils containing different As contamination levels. Compared to BC treatment, FMBC treatments significantly reduced As accumulation in different parts of the rice plants (P < 0.05), and FMBC 2 performed better than FMBC 1 did. Furthermore, exposure to 2% FMBC 2 decreased the total As concentration in the grain by 68.9-78.3%. The addition of FMBC increased the ratio of essential amino acids in the grain, decreased As availability in the soil, and significantly increased the Fe and Mn plaque contents. The reduced As accumulation in rice can be attributed to As(III) to As(V) oxidation by ferro - manganese binary oxide, which increased the As adsorbed by FMBC. Furthermore, Fe and Mn plaques on the rice root surface decreased the transport of As in rice. Taken together, our results demonstrated the applicability of FMBC as a potential measure for reducing As accumulation in rice, improving the amino acid content of rice grains, and effectively remediating As-polluted soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ferromagnetic phase in partially oxidized FeMn films

NASA Astrophysics Data System (ADS)

Svalov, A. V.; Savin, P. A.; Lepalovskij, V. N.; Vas'kovskiy, V. O.; Larrañaga, A.; Kurlyandskaya, G. V.

2018-04-01

The structure, magnetic and magnetoresistive properties of ferromagnetic phase in partially oxidized FeMn films was studied. The oxidation was performed by annealing of the samples under atmospheric pressure in a gas mixture (nitrogen with 0.5% oxygen) at the temperature of 300 °C. The resulting ferromagnetic phase was isotropic in the film plane. The value of the anisotropic magnetoresistance was similar to the value of the anisotropic magnetoresistance usually observed in films of pure iron. The oxidation of antiferromagnetic FeMn films resulted in the appearance of an exchange bias.

Effect of Ir-Mn composition on exchange bias and thermal stability of spin valves with nano-oxide layers

NASA Astrophysics Data System (ADS)

Liu, Y. F.; Cai, J. W.; Lai, W. Y.; Yu, G. H.

2008-05-01

The Ir-Mn bottom-pinned spin valves with nano-oxide layers (NOLs), Ta /Ni81Fe19/Ir-Mn/Co90Fe10/NOL/Co90Fe10/Cu/Co90Fe10/NOL/Ta, were fabricated by dc magnetron sputtering. The magnetoresistance (MR), magnetization, and exchange bias have been studied as a function of Ir-Mn composition and annealing temperature. It was observed that the spin valves with the Ir-Mn layer containing relatively low Mn content (58.9-72.4at.% Mn) show the best thermal endurance. For these samples, the Mn diffusion is effectively hampered by the NOL with a large MR value of about 12.5% even after annealing at 300°C. On the other hand, the exchange bias field of the pinned CoFe layer shows a maximum at Mn content of about 72.4at.%, which is different from the widely adopted composition, Ir-80at.% Mn, optimized from the top-pinned NiFe /Ir-Mn system. Moreover, the blocking temperature of the Ir -Mn/CoFe system with 72.4at.% Mn is higher than that with 80.6at.% Mn. The present results suggest that the Ir -Mn/CoFe pinning system with Mn content at about 72% renders the most favorable exchange bias and the best thermal stability for the bottom-pinned specular spin valves.

Oscillatory oxidation of Mn(II) ions by hexacyanoferrates(III) and bistability in the reductions of MnO 2 by hexacyanoferrates(II) in a CSTR

NASA Astrophysics Data System (ADS)

Olexová, Anna; Melicherčík, Milan; Treindl, L'udovít

1997-04-01

A new transition metal oscillator based on the oxidation of Mn 2+ ions by Fe(CN) 3-6 ions in a CSTR has been found. As well as the oscillations of the absorbance of the Mn(IV) species, pH-oscillations have been observed. In the reduction of manganese dioxide by Fe(CN) 4-6 ions a kinetic bistability has been described. A skeleton mechanism described recently for Mn(II)H 2O 2 and Mn(II)Br 2 oscillators has been applied here and further developed by the idea of the catalytic activity of colloidal particles and of the assistance of the pH-value change of both main processes, i.e. of the Mn(II) oxidation by Fe(CN) 3-6 ions and of the Mn(IV) reduction by Fe(CN) 4-6 ions. This appears to be the first case where both sides of a reversible reaction are autocatalytic.

Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation.

PubMed

Tang, Shoufeng; Yuan, Deling; Zhang, Qi; Liu, Yameng; Zhang, Qi; Liu, Zhengquan; Huang, Haiming

2016-09-01

A Fe-Mn bi-metallic oxide supported on granular activated carbon (Fe-Mn GAC) has been fabricated by an impregnation-desiccation method and tested in the catalytic ozonation of methyl orange (MO) degradation and mineralization. X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy characterizations revealed that Fe-Mn oxides were successfully loaded and uniformly distributed on the GAC, and nitrogen adsorption isotherms showed that the supported GAC retained a large surface area and a high pore volume compared with the pristine GAC. The catalytic activity was systematically assessed by monitoring the MO removal efficiencies at different operational parameters, such as catalyst dosage, initial solution pH, and ozone flow rate. The Fe-Mn GAC exhibited better catalytic activity relative to ozone alone and GAC alone, improving the TOC removal by 24.5 and 11.5 % and COD removal by 13.6 and 7.3 %, respectively. The reusability of the hybrid was examined over five consecutive cyclic treatments. The Fe-Mn GAC catalytic activity was only a slight loss in the cycles, showing good stability. The addition of Na2CO3 as hydroxyl radicals (•OH) scavengers proved that the catalytic ozonation mechanism was the enhanced generation of •OH by the Fe-Mn GAC. The above results render the Fe-Mn GAC an industrially promising candidate for catalytic ozonation of dye contaminant removal.

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

USGS Publications Warehouse

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.

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

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.

Manganese inhibition of microbial iron reduction in anaerobic sediments

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1988-01-01

Potential mechanisms for the lack of Fe(II) accumulation in Mn(IV)-containing anaerobic sediments were investigated. The addition of Mn(IV) to sediments in which Fe(II) reduction was the terminal electron-accepting process removed all the pore-water Fe(II), completely inhibited net Fe(III) reduction, and stimulated Mn(IV) reduction. Results demonstrate that preferential reduction of Mn(IV) by FE(III)-reducing bacteria cannot completely explain the lack of Fe(II) accumulation in anaerobic, Mn(IV)-containing sediments, and indicate that Mn(IV) oxidation of Fe(II) is the mechanism that ultimately prevents Fe(II) accumulation. -Authors

High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-09-01

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

On the nature of the Fe-bearing particles influencing hard anodizing behavior of AA 7075 extrusion products

NASA Astrophysics Data System (ADS)

Mukhopadhyay, A. K.

1998-03-01

The deleterious effects of Fe-bearing constituent particles on the fracture toughness of wrought A1 alloys have been known. Recent studies have shown that the presence of Fe-bearing, constituent particles is also determental to the nature and growth of the hard anodic oxide coating formed on such materials. The present study, using a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalysis (EPMA), was made to examine the influence of the nature of the Fe-bearing particles on the hard anodizing behavior of AA 7075 extrusion products containing varying amounts of Si, Mn, and Fe impurities. It was found that, in the alloy containing 0.25 wt pct Si, 0.27 wt pct Mn, and 0.25 wt pct Fe, the Fe-bearing constituent particles are based on the Al12(FeMn)3Si phase (bcc with α=1.260 nm). These particles survive the hard anodizing treatment, add resistance to the electrical path, causing a rapid rise in the bath voltage with time, and cause a nonuniform growth of the anodic oxide film. In the materials containing 0.05 wt pct Si, 0.04 wt pct Mn, and 0.18 wt pct Fe, on the other hand, the formation of the Al12(FeMn)3Si-based phase is suppressed, and two different Fe-bearing phases, based on Al-Fe-Cu-Mn-based (simple cubic with a=1.265 nm) and Al7Cu2Fe, respectively form. Neither the Al-Fe-Cu-Mn-based phase nor the Al7Cu2Fe-based phase survive the hard anodizing treatment, and this results in a steady rise in the bath voltage with time and a relatively uniform growth of the anodic oxide film. Consideration of the size of the Fe-bearing, particles reveals that the smaller the particle, the more uniform the growth of the anodic oxide film.

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

PubMed

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-01-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

Synthesis Gas Conversion over Rh-Based Catalysts Promoted by Fe and Mn

DOE PAGES

Liu, Yifei; Göeltl, Florian; Ro, Insoo; ...

2017-06-13

Rh/SiO2 catalysts promoted with Fe and Mn are selective for synthesis gas conversion to oxygenates and light hydrocarbons at 523 K and 580 psi. Selective anchoring of Fe and Mn species on Rh nanoparticles was achieved by controlled surface reactions and was evidenced by ultraviolet–visible absorption spectroscopy, scanning transmission electron microscopy, and inductively coupled plasma absorption emission spectroscopy. The interaction between Rh and Fe promotes the selective production of ethanol through hydrogenation of acetaldehyde and enhances the selectivity toward C2 oxygenates, which include ethanol and acetaldehyde. The interaction between Rh and Mn increases the overall reaction rate and the selectivitymore » toward C2+ hydrocarbons. The combination of Fe and Mn on Rh/SiO2 results in trimetallic Rh-Fe-Mn catalysts that surpass the performance of their bimetallic counterparts. The highest selectivities toward ethanol (36.9%) and C2 oxygenates (39.6%) were achieved over the Rh-Fe-Mn ternary system with a molar ratio of 1:0.15:0.10, as opposed to the selectivities obtained over Rh/SiO2, which were 3.5% and 20.4%, respectively. The production of value-added oxygenates and C2+ hydrocarbons over this trimetallic catalyst accounted for 55% of the total products. X-ray photoelectron spectroscopy measurements suggest that significant fractions of the Fe and Mn species exist as metallic iron and manganese oxides on the Rh surface upon reduction. These findings are rationalized by density functional theory (DFT) calculations, which reveal that the exact state of metals on the surfaces is condition-dependent, with Mn present as Mn(I) and Mn(II) oxide on the Rh (211) step edges and Fe present as Fe(I) oxide on the step edge and metallic subsurface iron on both Rh steps and terraces. CO Fourier transform infrared spectroscopy and DFT calculations suggest that the binding of CO to Rh (211) step edges modified by Fe and/or manganese oxide is altered in comparison to CO adsorption on a clean Rh (211) surface. These results suggest that Mn2Ox species and Fe and Fe2O modify bonding at Rh step edges and shift reaction selectivity away from CH4.« less

The role of biological uptake in iron and manganese cycling in Lake Baikal

USGS Publications Warehouse

Granina, L.Z.; Callender, E.

2006-01-01

The role of biological uptake in the internal cycling of Fe and Mn in Lake Baikal was quantified. Biological uptake, sedimentation consisting of the biogenic and lithogenic fluxes, and remineralization have been evaluated. The results of calculations show that about 5-10% of Fe and Mn accumulated in the lake are annually taken up by biota. More than 80% of this amount is again recycled after remineralization of biological material. At this, the biogenic fluxes of Fe and Mn are 2-4 times less compared to lithogenic ones. Thus not only is oxidation of Fe and Mn within the water column highly enriched in the oxygen that results in settling of Fe and Mn oxides, but also intensive biological uptake of these elements contributes to their fast removal from internal cycling. However, essential remineralization makes this process of minor importance to Fe and Mn cycling in Lake Baikal. ?? Springer 2006.

Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal.

PubMed

Ma, Zichuan; Zhao, Dongyuan; Chang, Yongfang; Xing, Shengtao; Wu, Yinsu; Gao, Yuanzhe

2013-10-21

Magnetic nanomaterials that can be easily separated and recycled due to their magnetic properties have received considerable attention in the field of water treatment. However, these nanomaterials usually tend to aggregate and alter their properties. Herein, we report an economical and environmentally friendly method for the synthesis of magnetic nanoparticles with core-shell structure. MnFe2O4 nanoparticles have been successfully coated with amorphous Mn-Co oxide shells. The synthesized MnFe2O4@Mn-Co oxide nanoparticles have highly negatively charged surface in aqueous solution over a wide pH range, thus preventing their aggregation and enhancing their performance for heavy metal cation removal. The adsorption isotherms are well fitted to a Langmuir adsorption model, and the maximal adsorption capacities of Pb(II), Cu(II) and Cd(II) on MnFe2O4@Mn-Co oxide are 481.2, 386.2 and 345.5 mg g(-1), respectively. All the metal ions can be completely removed from the mixed metal ion solutions in a short time. Desorption studies confirm that the adsorbent can be effectively regenerated and reused.

Nanostructured iron(III)-copper(II) binary oxide: a novel adsorbent for enhanced arsenic removal from aqueous solutions.

PubMed

Zhang, Gaosheng; Ren, Zongming; Zhang, Xiwang; Chen, Jing

2013-08-01

To obtain a highly efficient and low-cost adsorbent for arsenic removal from water, a novel nanostructured Fe-Cu binary oxide was synthesized via a facile co-precipitation method. Various techniques including BET surface area measurement, powder XRD, SEM, and XPS were used to characterize the synthetic Fe-Cu binary oxide. It showed that the oxide was poorly crystalline, 2-line ferrihydrite-like and was aggregated with many nanosized particles. Laboratory experiments were performed to investigate adsorption kinetics, adsorption isotherms, pH adsorption edge and regeneration of spent adsorbent. The results indicated that the Fe-Cu binary oxide with a Cu: Fe molar ratio of 1:2 had excellent performance in removing both As(V) and As(III) from water, and the maximal adsorption capacities for As(V) and As(III) were 82.7 and 122.3 mg/g at pH 7.0, respectively. The values are favorable, compared to those reported in the literature using other adsorbents. The coexisting sulfate and carbonate had no significant effect on arsenic removal. However, the presence of phosphate obviously inhibited the arsenic removal, especially at high concentrations. Moreover, the Fe-Cu binary oxide could be readily regenerated using NaOH solution and be repeatedly used. The Fe-Cu binary oxide could be a promising adsorbent for both As(V) and As(III) removal because of its excellent performance, facile and low-cost synthesis process, and easy regeneration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

NASA Astrophysics Data System (ADS)

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-10-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

PubMed

Goodwill, Joseph E; Mai, Xuyen; Jiang, Yanjun; Reckhow, David A; Tobiason, John E

2016-09-01

Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Biogeochemistry of Fe(II) oxidation in a photosynthetic microbial mat: Implications for Precambrian Fe(II) oxidation

NASA Astrophysics Data System (ADS)

Trouwborst, Robert E.; Johnston, Anne; Koch, Gretchen; Luther, George W.; Pierson, Beverly K.

2007-10-01

We studied the role of microbial photosynthesis in the oxidation of Fe(II) to Fe(III) in a high Fe(II) and high Mn(II) hot spring devoid of sulfide and atmospheric oxygen in the source waters. In situ light and dark microelectrode measurements of Fe(II), Mn(II) and O 2 were made in the microbial mat consisting of cyanobacteria and anoxygenic photosynthetic Chloroflexus sp. We show that Fe(II) oxidation occurred when the mat was exposed to varying intensities of sunlight but not near infrared light. We did not observe any Mn(II) oxidation under any light or dark condition over the pH range 5-7. We observed the impact of oxygenic photosynthesis on Fe(II) oxidation, distinct from the influence of atmospheric O 2 and anoxygenic photosynthesis. In situ Fe(II) oxidation rates in the mats and cell suspensions exposed to light are consistent with abiotic oxidation by O 2. The oxidation of Fe(II) to form primary Fe(III) phases contributed to banded iron-formations (BIFs) during the Precambrian. Both oxygenic photosynthesis, which produces O 2 as an oxidizing waste product, and anoxygenic photosynthesis in which Fe(II) is used to fix CO 2 have been proposed as Fe(II) oxidation mechanisms. Although we do not know the specific mechanisms responsible for all Precambrian Fe(II) oxidation, we assessed the relative importance of both mechanisms in this modern hot spring environment. In this environment, cyanobacterial oxygen production accounted for all the observed Fe(II) oxidation. The rate data indicate that a modest population of cyanobacteria could have mediated sufficient Fe(II) oxidation for some BIFs.

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine.

PubMed

Akob, Denise M; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-08-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Identification of Mn(II)-Oxidizing Bacteria from a Low-pH Contaminated Former Uranium Mine

PubMed Central

Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. PMID:24928873

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine

USGS Publications Warehouse

Akob, Denise M.; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments.

Efficient photocatalytic oxidation of arsenite from contaminated water by Fe2O3-Mn2O3 nanocomposite under UVA radiation and process optimization with experimental design.

PubMed

Eslami, Hadi; Ehrampoush, Mohammad Hassan; Esmaeili, Abbas; Ebrahimi, Ali Asghar; Salmani, Mohammad Hossein; Ghaneian, Mohammad Taghi; Falahzadeh, Hossein

2018-09-01

The efficiency of photocatalytic oxidation process in arsenite (As(III)) removal from contaminated water by a new Fe 2 O 3 -Mn 2 O 3 nanocomposite under UV A radiation was investigated. The effect of nanocomposite dosage, pH and initial As(III) concentration on the photocatalytic oxidation of As(III) were studied by experimental design. The synthesized nanocomposite had a uniform and spherical morphological structure and contained 49.83% of Fe 2 O 3 and 29.36% of Mn 2 O 3 . Based on the experimental design model, in photocatalytic oxidation process, the effect of pH was higher than other parameters. At nanocomposite concentrations of more than 12 mg L -1 , pH 4 to 6 and oxidation time of 30 min, photocatalytic oxidation efficiency was more than 95% for initial As(III) concentration of less than 500 μg L -1 . By decreasing pH and increasing the nanocomposite concentration, the photocatalytic oxidation efficiency was increased. Furthermore, by increasing the oxidation time from 10 to 240 min, in addition to oxidation of As(III) to arsenate (As(V)), the residual As(V) was adsorbed on the Fe 2 O 3 -Mn 2 O 3 nanocomposite and total As concentration was decreased. Therefore, Fe 2 O 3 -Mn 2 O 3 nanocomposite as a bimetal oxide, at low doses and short time, can enhance and improve the efficiency of the photocatalytic oxidation and adsorption of As(III) from contaminated water resources. Furthermore, the energy and material costs of the UV A /Fe 2 O 3 -Mn 2 O 3 system for photocatalytic oxidation of 1  mg L -1 As(III) in the 1 L laboratory scale reactor was 0.0051 €. Copyright © 2018 Elsevier Ltd. All rights reserved.

Synthesis and Microstructural Characterization of Manganese Oxide Electrodes for Application as Electrochemical Supercapacitors

NASA Astrophysics Data System (ADS)

Babakhani, Banafsheh

The aim of this thesis work was to synthesize Mn-based oxide electrodes with high surface area structures by anodic electrodeposition for application as electrochemical capacitors. Rod-like structures provide large surface areas leading to high specific capacitances. Since templated electrosynthesis of rods is not easy to use in practical applications, it is more desirable to form rod-like structures without using any templates. In this work, Mn oxide electrodes with rod-like structures (˜1.5 µm in diameter) were synthesized from a solution of 0.01 M Mn acetate under galvanostatic control without any templates, on Au coated Si substrates. The electrochemical properties of the synthesized nanocrystalline electrodes were investigated to determine the effect of morphology, chemistry and crystal structure on the corresponding electrochemical behavior of Mn oxide electrodes. Mn oxides prepared at different current densities showed a defective antifluoritetype crystal structure. The rod-like Mn oxide electrodes synthesized at low current densities (5 mAcm.2) exhibited a high specific capacitance due to their large surface areas. Also, specific capacity retention after 250 cycles in an aqueous solution of 0.5 M Na2SO4 at 100 mVs -1 was about 78% of the initial capacity (203 Fg-1 ). To improve the electrochemical capacitive behavior of Mn oxide electrodes, a sequential approach and a one-step method were adopted to synthesize Mn oxide/PEDOT electrodes through anodic deposition on Au coated Si substrates from aqueous solutions. In the former case, free standing Mn oxide rods (about 10 µm long and less than 1.5 µm in diameter) were first synthesized, then coated by electro-polymerization of a conducting polymer (PEDOT) giving coaxial rods. The one-step, co-electrodeposition method produced agglomerated Mn oxide/PEDOT particles. The electrochemical behavior of the deposits depended on the morphology and crystal structure of the fabricated electrodes, which were affected by the composition and pH of the electrolyte, temperature, current density and polymer deposition time. Mn oxide/PEDOT coaxial core/shell rods consisted of MnO2 with an antifluorite-type structure coated with amorphous PEDOT. The Mn oxide/PEDOT coaxial core/shell electrodes prepared by the sequential method showed significantly better specific capacity and redox performance properties relative to both uncoated Mn oxide rods and co- electrodeposited Mn oxide/PEDOT electrodes. The best specific capacitance for Mn oxide/PEDOT rods produced sequentially was ˜295 F g-1 with ˜92% retention after 250 cycles in 0.5 M Na2SO4 at 100 mV s-1. To further improve the electrochemical capacitive behavior of Mn oxide electrodes, Co-doped and Fe-doped Mn oxide electrodes with a rod-like morphology and antifluorite-type crystal structure were synthesized by anodic electrodeposition, on Au coated Si substrates, from dilute solutions of Mn acetate and Co sulphate and Mn acetate and Fe chloride. Also, Mn-Co oxide/PEDOT coaxial core/shell rods were synthesized by applying a shell of PEDOT on Mn-Co oxide electrodes. Mn-Co oxide/PEDOT electrodes consisted of MnO2, with partial Co 2+ and Co3+ ion substitution for Mn4+, and amorphous PEDOT. Mn-Fe oxide electrodes consisted of MnO2, with partial Fe2+ and Fe3+ ion substitution for Mn4+. Electrochemical analysis showed that the capacitance values for all deposits increased with increasing scan rate to 100 mVs -1, and then decreased after 100 mVs-1. The Mn-Co oxide/PEDOT electrodes showed improved specific capacity and electrochemical cyclability relative to uncoated Mn-Co oxides and Mn-Fe oxides. Mn-Co oxide/PEDOT electrodes with rod-like structures had high capacitances (up to 310 Fg -1) at a scan rate of 100 mVs-1 and maintained their capacitance after 500 cycles in 0.5 M Na2SO4 (91% retention). Capacitance reduction for the deposits was mainly due to the loss of Mn ions by dissolution in the electrolyte solution. To better understand the nucleation and growth mechanisms of Mn oxide electrodes, the effects of supersaturation ratio on the morphology and crystal structure of electrodeposited Mn oxide were studied. By changing deposition parameters, including deposition current density, electrolyte composition, pH and temperature, a series of nanocrystalline Mn oxide electrodes with various morphologies (continuous coatings, rod-like structures, aggregated rods and thin sheets) and an antifluorite-type crystal structure was obtained. Mn oxide thin sheets showed instantaneous nucleation and single crystalline growth; rods had a mix of instantaneous/progressive nucleation and polycrystalline growth and continuous coatings formed by progressive nucleation and polycrystalline growth. Electrochemical analysis revealed the best capacitance behaviour obtained for Mn oxide thin sheets followed by Mn oxide rods, with dimensions on the microscale, and then continuous coatings. The highest specific capacitance (˜230 Fg-1) and capacitance retention rates (˜88%) were obtained for Mn oxide thin sheets after 250 cycles in 0.5 M Na2 SO4 at 20 mVs-1.

Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

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.

Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon

NASA Astrophysics Data System (ADS)

Xiong, Ying; Tong, Qiang; Shan, Weijun; Xing, Zhiqiang; Wang, Yuejiao; Wen, Siqi; Lou, Zhenning

2017-09-01

Iron hydroxide/manganese dioxide doped straw activated carbon was synthesized for As(III) adsorption. The Fe-Mn-SAc adsorbent has two advantages, on the one hand, the straw active carbon has a large surface area (1360.99 m2 g-1) for FeOOH and MnO2 deposition, on the other hand, the manganese dioxide has oxidative property as a redox potential of (MnO2 + H+)/Mn2+, which could convert As(III) into As(V). Combined with the arsenic species after reacting with Fe-Mn-SAc, the As(III) transformation and adsorption mechanism was discussed. H2AsO4-oxidized from As(III) reacts with the Fe-Mn-SAc by electrostatic interaction, and unoxidized As(III) as H3AsO3 reacts with SAc and/or iron oxide surface by chelation effect. The adsorption was well-described by Langmuir isotherms model, and the adsorption capacity of As(III) was 75.82 mg g-1 at pH 3. Therefore, considering the straw as waste biomass material, the biosorbent (Fe-Mn-SAc) is promising to be exploited for applications in the treatment of industrial wastewaters containing a certain ratio of arsenic and germanium.

PSEUDO-BINARY SYSTEMS INVOLVING RARE EARTH LAVES PHASES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wernick, J.H.; Haszko, S.E.; Dorsi, D.

1962-06-01

The phase relations in a number of pseudo-binary systems involving rare earth Laves phases were determined. Complete series of cubic solid-solutions occur in the DyMn/sub 2/HoMn/sub 2/, HoMn/sub 2/-HoFe/sub 2/, DyMn/sub 2/-DyFe/ sub 2/, HoMn/sub 2/-HoAl/ sub 2/, TbMn/sub 2/TbAl/sub 2/, and DyMn/sub 2/-DyAl/ sub 2/ pseudobinary systems. Deviations from linearity in the lattice constants with composition occur in all these systems. Complete series of cubic solidsolutions also exist in the GdAl/sub 2/-ErAl/sub 2/, GdAl/sub 2/-PrAl/sub 2/ , GdAl/sub 2/-NdAl/sub 2/, GdAl/sub 2/-DyAl/sub 2/, TbAl/sub 2/-NdAl/sub 2/, and T bAl/sub 2/-DyAl/sub 2/ systems. For these systems, no deviation from linearitymore » occurs in the lattice constants. For the DyFe/sub 2/-DyAl/sub 2/ and DyCo/sub 2/- DyAl/sub 2/ systems, two new ternary phases, DyFeAl and DyCoAl, form and have the MgZn/sub 2/ structure. Their structures were determined from x-ray powder data only. The electronic state giving rise to the formation of these ternary phases is discussed qualitatively. For the DyMn/sub 2/TmMn/sub 2/ system, the range of composition in which the cubic MgCu/sub 2/ and hexagonal MgZn/sub 2/ structures exist are reported. No complete series of solid solutions or intermediate phases are formed in the DyNi/sub 2/-DyAl/sub 2/ system. (auth)« less

Triple-mixture of Zn, Mn, and Fe increases bioaccumulation and causes oxidative stress in freshwater neotropical fish.

PubMed

de Oliveira, Luciana Fernandes; Santos, Caroline; Risso, Wagner Ezequiel; Dos Reis Martinez, Claudia Bueno

2018-06-01

Metal bioaccumulation and oxidative stress biomarkers were determined in Prochilodus lineatus to understand the effects of short-term exposure to a triple-mixture of Zn, Mn, and Fe. Three independent tests were carried out, in which fish were exposed to 3 concentrations of Zn (0.18, 1.0, and 5.0 mg L -1 ), Mn (0.1, 0.5, and 5.0 mg L -1 ), and in the mix test to Fe (5.0 mg L -1 ) and a mixture of Zn (1.0 mg L -1 ) + Mn (0.5 mg L -1 ), with and without Fe. After exposure for 96 h, tissues were removed for metal bioaccumulation analysis and oxidative stress biomarkers were determined in liver, along with DNA damage in blood cells. Our results revealed that Zn and Mn were bioaccumulated in fish tissues after exposure to 5.0 mg L -1 , whereas Fe only bioaccumulated in muscle and gills after mixture exposure. Results indicated that 1 metal interfered with the other's bioaccumulation. In P. lineatus, 5 mg L -1 of both Mn and Fe were toxic, because damage was observed (lipid peroxidation [LPO] in liver and DNA damage in blood cells), whereas Zn induced liver responses (metallothionein [MT] and reduced glutathione [GSH] increases) to prevent damage. In terms of bioaccumulation and alterations of oxidative stress biomarkers, we showed that Zn, Mn, and Fe triple-mixture enhances individual metal toxicity in Neotropical fish P. lineatus. Environ Toxicol Chem 2018;37:1749-1756. © 2018 SETAC. © 2018 SETAC.

New understanding on separation of Mn and Fe from ferruginous manganese ores by the magnetic reduction roasting process

NASA Astrophysics Data System (ADS)

Liu, Bingbing; Zhang, Yuanbo; Wang, Juan; Wang, Jia; Su, Zijian; Li, Guanghui; Jiang, Tao

2018-06-01

Magnetic reduction roasting followed by magnetic separation process is reported as a simple route to realize separation of Mn and Fe from ferruginous manganese ores (Fe-Mn ores). However, the separation and recovery of Mn and Fe oxides are not very effective. This work clarified the underlying reason for the poor separation and also proposed some suggestions for the magnetic reduction process. In this work, the effect of temperature on the magnetic reduction roasting - magnetic separation of Fe-Mn ore was investigated firstly. Then the reduction behaviors of MnO2-Fe2O3 system and MnO2-Fe2O3-10 wt.%SiO2 system under 10 vol.% CO-90 vol.% CO2 at 600-1000 °C were investigated by XRD, XPS, SEM-EDS, VSM, DSC and thermodynamics analyses. Reduction and separation tests showed that higher reduction temperature was beneficial to the recovery of iron while it's not in favor of the recovery of manganese when the temperature was over 800 °C. The formation of composite oxide MnxFe3-xO4 with strong magnetism between the interface of the MnO2 and Fe2O3 particles leaded to the poor separation of iron and manganese. In addition, the formation mechanism of MnxFe3-xO4 from MnO2 and Fe2O3 as well as the interface reaction reduced under 10 vol.% CO was discussed in this study. Finally, some suggestions were recommended for the magnetic reduction roasting for utilizing the Fe-Mn ores effectively.

Dissimilatory Fe(III) reduction by the marine microorganism Desulfuromonas acetoxidans

USGS Publications Warehouse

Roden, E.E.; Lovley, D.R.

1993-01-01

The ability of the marine microorganism Desulfuromonas acetoxidans to reduce Fe(III) was investigated because of its close phylogenetic relationship with the freshwater dissimilatory Fe(III) reducer Geobacter metallireducens. Washed cell suspensions of the type strain of D. acetoxidans reduced soluble Fe(III)-citrate and Fe(III) complexed with nitriloacetic acid. The c-type cytochrome(s) of D. acetoxidans was oxidized by Fe(III)- citrate and Mn(IV)-oxalate, as well as by two electron acceptors known to support growth, colloidal sulfur and malate. D. acetoxidans grew in defined anoxic, bicarbonate-buffered medium with acetate as the sole electron donor and poorly crystalline Fe(III) or Mn(IV) as the sole electron acceptor. Magnetite (Fe3O4) and siderite (FeCO3) were the major end products of Fe(III) reduction, whereas rhodochrosite (MnCO3) was the end product of Mn(IV) reduction. Ethanol, propanol, pyruvate, and butanol also served as electron donors for Fe(III) reduction. In contrast to D. acetoxidans, G. metallireducens could only grow in freshwater medium and it did not conserve energy to support growth from colloidal S0 reduction. D. acetoxidans is the first marine microorganism shown to conserve energy to support growth by coupling the complete oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). Thus, D. acetoxidans provides a model enzymatic mechanism for Fe(III) or Mn(IV) oxidation of organic compounds in marine and estuarine sediments. These findings demonstrate that 16S rRNA phylogenetic analyses can suggest previously unrecognized metabolic capabilities of microorganisms.

Pathways of organic carbon oxidation in three continental margin sediments

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Jorgensen, B. B.; Fossing, H.; Glud, R.; Gundersen, J.; Ramsing, N. B.; Thamdrup, B.; Hansen, J. W.; Nielsen, L. P.; Hall, P. O.

1993-01-01

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

The anaerobic degradation of organic matter in Danish coastal sediments - Iron reduction, manganese reduction, and sulfate reduction

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Thamdrup, BO; Hansen, Jens W.

1993-01-01

A combination of porewater and solid phase analysis as well as a series of sediment incubations are used to quantify organic carbon oxidation by dissimilatory Fe reduction, Mn reduction, and sulfate reduction, in sediments from the Skagerrak (located off the northeast coast of Jutland, Denmark). Solid phase data are integrated with incubation results to define the zones of the various oxidation processes. At S(9), surface Mn enrichments of up to 3.5 wt pct were found, and with such a ready source of Mn, dissimilatory Mn reduction was the only significant anaerobic process of carbon oxidation in the surface 10 cm of the sediment. At S(4) and S(6), active Mn reduction occurred; however, most of the Mn reduction may have resulted from the oxidation of acid volatile sulfides and Fe(2+) rather than by a dissimilatory sulfate. Dissolved Mn(2+) was found to completely adsorb onto sediment containing fully oxidized Mn oxides.

Novel Co- or Ni-Mn binary oxide catalysts with hydroxyl groups for NH3-SCR of NOx at low temperature

NASA Astrophysics Data System (ADS)

Gao, Fengyu; Tang, Xiaolong; Yi, Honghong; Zhao, Shunzheng; Wang, Jiangen; Shi, Yiran; Meng, Xiaomi

2018-06-01

Novel hydroxyl-containing Me-Mn binary oxides (Me = Co, Ni) were prepared for the selective catalytic reduction of NOx with NH3 by a combined complexation-esterification method. The binary oxides of Co-MnOx and Ni-MnOx with mixed crystal phases of Mn3O4 and Co3O4, Mn2O3 and NiMnO3 were obtained at 550 °C. SCR activity decreased in the order of Mn3O4-Co3O4-OH > Mn2O3-NiMnO3-OH > Mn2O3-OH > Mn3O4-OH, benefiting from the high concentration of chemisorbed oxygen and effective electron transformation of cations. Mn2O3-containing catalysts had better selectivity to N2 than those containing Mn3O4. Higher selectivity to N2O over Mn3O4-containing catalysts was attributed to the depth dehydrogenation of coordinated NH3 by the active oxygen species with lower Mnsbnd O band energy. The typical Eley-Rideal mechanism over Mn3O4-OH and Mn3O4-Co3O4-OH, and the additional formation pathway of NH4NO3 species over Mn2O3-OH and Mn2O3-NiMnO3-OH catalysts were proposed via the in-situ DRIFTS experiments. Although the Co and Ni elements had a good role in delaying the poisoning of SO2, these catalysts were eventually sulfated by SO2 over the postponement, which might due to the metal sulfate and ammonia hydrogensulfite species.

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Design of template-stabilized active and earth-abundant oxygen evolution catalysts in acid† †Electronic supplementary information (ESI) available: CVs for unary metal oxides deposition, electrochemical stability at higher current densities for unary metal oxides at pH 2.5, EDS maps for CoMnOx and CoPbOx, STEM images and PXRD of CoMnOx and CoFePbOx, high-resolution XPS of Fe 2p for CoFePbOx, Pourbaix diagrams (of Mn, Co, Pb, and Fe), and elemental analysis. See DOI: 10.1039/c7sc01239j Click here for additional data file.

PubMed Central

Huynh, Michael; Ozel, Tuncay; Liu, Chong; Lau, Eric C.

2017-01-01

Oxygen evolution reaction (OER) catalysts that are earth-abundant and are active and stable in acid are unknown. Active catalysts derived from Co and Ni oxides dissolve at low pH, whereas acid stable systems such as Mn oxides (MnOx) display poor OER activity. We now demonstrate a rational approach for the design of earth-abundant catalysts that are stable and active in acid by treating activity and stability as decoupled elements of mixed metal oxides. Manganese serves as a stabilizing structural element for catalytically active Co centers in CoMnOx films. In acidic solutions (pH 2.5), CoMnOx exhibits the OER activity of electrodeposited Co oxide (CoOx) with a Tafel slope of 70–80 mV per decade while also retaining the long-term acid stability of MnOx films for OER at 0.1 mA cm–2. Driving OER at greater current densities in this system is not viable because at high anodic potentials, Mn oxides convert to and dissolve as permanganate. However, by exploiting the decoupled design of the catalyst, the stabilizing structural element may be optimized independently of the Co active sites. By screening potential–pH diagrams, we replaced Mn with Pb to prepare CoFePbOx films that maintained the high OER activity of CoOx at pH 2.5 while exhibiting long-term acid stability at higher current densities (at 1 mA cm–2 for over 50 h at pH 2.0). Under these acidic conditions, CoFePbOx exhibits OER activity that approaches noble metal oxides, thus establishing the viability of decoupling functionality in mixed metal catalysts for designing active, acid-stable, and earth-abundant OER catalysts. PMID:29163926

Structural and electrochemical properties of iron- and nickel-substituted Li2MnO3 cathodes in charged and discharged states

NASA Astrophysics Data System (ADS)

Yuge, Ryota; Kuroshima, Sadanori; Toda, Akio; Miyazaki, Takashi; Tabuchi, Mitsuharu; Doumae, Kyosuke; Shibuya, Hideka; Tamura, Noriyuki

2017-10-01

Structural change and the charge compensation mechanism of lithium-rich layered cathode (Li1.23Fe0.15Ni0.15Mn0.46O2) in charged and discharged states were investigated. Selected area electron diffraction analysis revealed that in discharged state, an initial structure composed of a single phase of monoclinic layered rock-salt changed to a mixture of hexagonal layered rock-salt and spinel-like structures. In charged state, the spinel-like phase became dominant as transition-metal ions migrate. 57Fe Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), and Soft-XAS showed that the valence of Fe and Ni ions approximately changed from Fe3+ to Fe3.2+ and Ni2+ to Ni3.5+ during charge-discharge, although Mn ions remained as Mn4+. Various oxidation states of oxide ions such as superoxide, peroxide, and hole states have also been detected in charged state. Considering that actual discharge capacity was 255 mAh/g, the contribution to charge compensation from the valence change of Fe and Ni ions was extremely small, and it only contributed to about one-third of total capacity. Therefore, the mechanism to yield high capacity of the Li1.23Fe0.15Ni0.15Mn0.46O2 cathode relates strongly to the redox reaction of oxide ions. Moreover, the decrease in capacity during charge-discharge cycling was mainly due to the irreversible redox reaction of Mn, Fe, and oxide ions.

Micro/nanostructured porous Fe-Ni binary oxide and its enhanced arsenic adsorption performances.

PubMed

Liu, Shengwen; Kang, Shenghong; Wang, Guozhong; Zhao, Huijun; Cai, Weiping

2015-11-15

A simple method is presented to synthesize micro/nano-structured Fe-Ni binary oxides based on co-precipitation and subsequent calcination. It has been found that the Fe-Ni binary oxides are composed of the porous microsized aggregates built with nanoparticles. When the atomic ratio of Fe to Ni is 2 to 1 the binary oxide is the micro-scaled aggregates consisting of the ultrafine NiFe2O4 nanoparticles with 3-6nm in size, and shows porous structure with pore diameter of 3nm and a specific surface area of 245m(2)g(-1). Such material is of abundant surface functional groups and has exhibited high adsorption performance to As(III) and As(V). The kinetic adsorption can be described by pseudo-second order model and the isothermal adsorption is subject to Langmuir model. The maximum adsorption capacity on such Fe-Ni porous binary oxide is up to 168.6mgg(-1) and 90.1mgg(-1) for As(III) and As(V), respectively, which are much higher than the arsenic adsorption capacity for most commercial adsorbents. Such enhanced adsorption ability for this material is mainly attributed to its porous structure and high specific surface area as well as the abundant surface functional groups. Further experiments have revealed that the influence of the anions such as sulfate, carbonate, and phosphate, which commonly co-exist in water, on the arsenic adsorption is insignificant, exhibiting strong adsorption selectivity to arsenic. This micro/nano-structured porous Fe-Ni binary oxide is hence of good practicability to be used as a highly efficient adsorbent for arsenic removal from the real arsenic-contaminated waters. Copyright © 2015 Elsevier Inc. All rights reserved.

Enhancement of magnetic ordering temperature in iron substituted ytterbium manganate (YbMn{sub 1-x}Fe{sub x}O{sub 3})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samal, S.L.; Magdaleno, T.; Ramanujachary, K.V.

Oxides of the type YbMn{sub 1-x}Fe{sub x}O{sub 3}; x<=0.3 showing multiferroic behavior have been synthesized by the solid state route. These oxides crystallize in the hexagonal structure known for the parent YbMnO{sub 3} with the c/a ratio increasing with Fe substitution. The distortion of the MnO{sub 5} polyhedra (tbp) decreases and the Mn-O-Mn bonds in the a-b plane become shorter with Fe-substitution. Magnetic ordering is observed from the low temperature neutron diffraction study. The compounds were found to be antiferromagnetic and the ordering temperature T{sub N} increased from 82 K for pure YbMnO{sub 3} to 95 K for YbMn{sub 0.7}Fe{submore » 0.3}O{sub 3}. Variable temperature dielectric measurements (15-110 K) show an anomaly in the dielectric constant at temperatures close to the antiferromagnetic ordering temperature for all the compositions, showing a unique correlation between the magnetic and electric field. The increase in the ordering temperature in YbMn{sub 1-x}Fe{sub x}O{sub 3} is explained on the basis of increase in covalence of Mn/Fe-O-Mn/Fe bonds (shorter) with iron substitution. - Graphical abstract: Hexagonal manganites of the type YbMn{sub 1-x}Fe{sub x}O{sub 3}; x<=0.3 have been synthesized by the solid state route. The distortion of the MnO{sub 5} polyhedra (tbp) decreases and the Mn-O-Mn bonds in the a-b plane become shorter with Fe-substitution. The compounds were found to be antiferromagnetic and the ordering temperature T{sub N} increased from 82 K for pure YbMnO{sub 3} to 95 K for YbMn{sub 0.7}Fe{sub 0.3}O{sub 3}. The increase in the ordering temperature in YbMn{sub 1-x}Fe{sub x}O{sub 3} is explained on the basis of increase in covalence of Mn/Fe-O-Mn/Fe bonds with iron substitution. Low temperature dielectric measurements show a unique correlation between the magnetic and electric fields for all compositions.« less

Effect of Heat-Treatment Temperature on the Interfacial Reaction Between Oxide Inclusions and Si-Mn Killed Steel

NASA Astrophysics Data System (ADS)

Zhang, Xueliang; Yang, Shufeng; Liu, Chengsong; Li, Jingshe; Hao, Weixing

2018-06-01

The effect of heat-treatment temperature on the interfacial reaction between MnO-SiO2-FeO oxide and Fe-Mn-Si alloy was investigated by the diffusion couple method in the temperature range of 1173-1573 K. The reaction at the interface between the alloy and oxide was not obvious during treatment at 1173 K, but, with increasing heat-treatment temperature, the interfacial reaction was strengthened and the proportion of the MnO·SiO2 phase in the oxide increased. The width of the particle-precipitation zone in the alloy increased with increasing temperature from 1173 K to 1473 K but decreased at 1573 K owing to coarsening of the precipitated particles. In addition, Mn2+ and Si4+ in the oxide significantly diffused into the alloy at 1573 K, resulting in an obvious increase of the Mn and Si contents in the alloy near the interface.

High Curie temperature of Ce-Fe-Si compounds with ThMn12 structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, C; Pinkerton, FE; Herbst, JF

2015-01-15

We report the discovery of ternary CeFe(12-x)Si(x)compounds possessing the ThMn12 structure. The samples were prepared by melt spinning followed by annealing. In contrast to other known Ce Fe-based binary and ternary compounds, CeFe12-xSix compounds exhibit exceptionally high Curie temperatures whose values increase with added Si substitution. The highest T. = 583 K in CeFe10Si2 rivals that of the well-established Nd2Fe14B compound. We ascribe the T-c behavior to a combination of Si-induced 3d band structure changes and partial Ce3+ stabilization. (C) 2014 Published by Elsevier Ltd.

Electron induced surface reactions of (η5-C5H5)Fe(CO)2Mn(CO)5, a potential heterobimetallic precursor for focused electron beam induced deposition (FEBID).

PubMed

Unlu, Ilyas; Spencer, Julie A; Johnson, Kelsea R; Thorman, Rachel M; Ingólfsson, Oddur; McElwee-White, Lisa; Fairbrother, D Howard

2018-03-14

Electron-induced surface reactions of (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 were explored in situ under ultra-high vacuum conditions using X-ray photoelectron spectroscopy and mass spectrometry. The initial step involves electron-stimulated decomposition of adsorbed (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 molecules, accompanied by the desorption of an average of five CO ligands. A comparison with recent gas phase studies suggests that this precursor decomposition step occurs by a dissociative ionization (DI) process. Further electron irradiation decomposes the residual CO groups and (η 5 -C 5 H 5 , Cp) ligand, in the absence of any ligand desorption. The decomposition of CO ligands leads to Mn oxidation, while electron stimulated Cp decomposition causes all of the associated carbon atoms to be retained in the deposit. The lack of any Fe oxidation is ascribed to either the presence of a protective carbonaceous matrix around the Fe atoms created by the decomposition of the Cp ligand, or to desorption of both CO ligands bound to Fe in the initial decomposition step. The selective oxidation of Mn in the absence of any Fe oxidation suggests that the fate of metal atoms in mixed-metal precursors for focused electron beam induced deposition (FEBID) will be sensitive to the nature and number of ligands in the immediate coordination sphere. In related studies, the composition of deposits created from (η 5 -C 5 H 5 )Fe(CO) 2 Mn(CO) 5 under steady state deposition conditions, representative of those used to create nanostructures in electron microscopes, were measured and found to be qualitatively consistent with predictions from the UHV surface science studies.

The oxidation state of iron and manganese in polymetallic nodules from the Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Ganwani, Girish; Meena, Samay Singh; Ram, Sahi; Bijlani, N.; Bhatia, Beena; Tripathi, R. P.

2018-05-01

The study of oxidation states of iron (Fe) and manganese (Mn) in polymetallic nodules were carried out by means of X-ray photoelectron spectroscopic techniques. The polymetallic nodules were collected from different locations of the Central Indian Ocean Basin (CIOB). The Mn/Fe ratio allowed the differentiation of these nodules from their origin: "hydrogeneous" or "hydrothermal". The binding energies of Mn 2p3/2 (ranging from 641.5 to 642.4 ev), Fe 2p3/2 (ranging from 711.0 to 711.8 ev) and O 1s (ranging from 530.2 to 530.9 ev) from XPS reveal that most of manganese is in Mn4+ and iron is in Fe3+ state.

Giant magnetoresistance enhancement in spin valves with nano-oxide layers

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Chen, C. J.; Chin, T. S.

2001-06-01

The magnetoresistance (MR) ratio is enhanced by 35% by inserting the nano-oxide layer (NOL) at the Ta/Co interface in the FeMn-based top spin valves (Ta/NOL/Co/Cu/Co/FeMn/Ta). The enhancement is attributed to specular reflection, resulting in a large resistance change and small sheet resistance. However, the formation of NOL at the interface of Ta/Co suppresses the (111) texture, resulting in small exchange fields. Top spin valves with NOLs show good thermal stability up to 200 °C annealing. The MR ratio is further increased after annealing at temperatures below 200 °C. Enhancement of the MR ratio by 61% can be achieved by annealing at 150 °C. For bottom spin valves (Ta/NiFe/FeMn/Co/Cu/NiFe/Ta), NOLs formed at FeMn/Co and NiFe/Ta interfaces increase MR ratios, but NOLs at Co/Cu or Cu/NiFe deteriorate the differential spin scattering and significantly reduce MR ratios.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Štengl, Václav, E-mail: stengl@iic.cas.cz; J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem; Grygar, Tomáš Matys

Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electronmore » microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.« less

Iron, Manganese and Copper Release from Synthetic Hydroxyapatite

NASA Technical Reports Server (NTRS)

Sutter, B.; Hossner, L. R.; Ming, Douglas W.

1999-01-01

Kinetic stir-flow dissolution experiments were performed on iron- (Fe-SHA), manganese- (Mn-SHA), and copper- (Cu-SHA) containing synthetic hydroxyapatites. Solution treatments consisted of de-ionized water, citric acid and DTPA. Initially, Mn concentrations were higher than Cu concentrations and Fe concentrations were the lowest in all treatments. At later times Mn and Cu concentrations dropped in the DTPA treatment while Fe rose to the concentration similar to Mn and Cu. At all times, metal release concentrations in the water and citric acid treatments followed the trend of Mn>Cu>Fe. Rietveld analysis of x-ray diffraction data and ^31P NMR indicated that the metals substituted for Ca in the SHA structure. However, EPR data suggested that a metal (hydr)oxide phase existed either on the SHA surface or between the SHA crystallites. The metal concentration trend of Mn>Cu>Fe suggested that the initial solution metal concentrations are dependent on the dissolution of (hydr)oxides from SHA surfaces or between SHA crystallites. Similar metal concentrations at later times in the DTPA experiments suggests that metal concentrations were controlled by the release of Mn, Cu, or Fe from the SHA structure.

Review of Manganese Processing for Production of TRIP/TWIP Steels, Part 2: Reduction Studies

NASA Astrophysics Data System (ADS)

Elliott, R.; Coley, K.; Mostaghel, S.; Barati, M.

2018-02-01

Production of ultrahigh-manganese steels is expected to result in significant increase in demand for low-carbon (LC) ferromanganese (FeMn) and silicomanganese (SiMn). Current manganese processing techniques are energy intensive and typically yield a high-carbon product. The present work therefore reviews available literature regarding carbothermic reduction of Mn oxides and ores, with the objective of identifying opportunities for future process development to mitigate the cost of LC FeMn and SiMn. In general, there is consensus that carbothermic reduction of Mn oxides and ores is limited by gasification of carbon. Conditions which enhance or bypass this step (e.g., by application of CH4) show higher rates of reduction at lower temperatures. This phenomenon has potential application in solid-state reduction of Mn ore. Other avenues for process development include optimization of the prereduction step in conventional FeMn production and metallothermic reduction as a secondary reduction step.

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

PubMed Central

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

2013-01-01

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

PubMed

Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

2013-05-28

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds

NASA Astrophysics Data System (ADS)

Liu, Yangzhen; Xing, Jiandong; Fu, Hanguang; Li, Yefei; Sun, Liang; Lv, Zheng

2017-08-01

The properties of sulfides are important in the design of new iron-steel materials. In this study, first-principles calculations were used to estimate the structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds. The results reveal that these XS binary compounds are thermodynamically stable, because their formation enthalpy is negative. The elastic constants, Cij, and moduli (B, G, E) were investigated using stress-strain and Voigt-Reuss-Hill approximation, respectively. The sulfide anisotropy was discussed from an anisotropic index and three-dimensional surface contours. The electronic structures reveal that the bonding characteristics of the XS compounds are a mixture of metallic and covalent bonds. Using a quasi-harmonic Debye approximation, the heat capacity at constant pressure and constant volume was estimated. NiS possesses the largest CP and CV of the sulfides.

Binary Mixtures of Permanganate and Chlorinated Volatile Organic Compounds in Groundwater Samples: Sample Preservation and Analysis

EPA Science Inventory

Ground water samples collected at sites where in-situ chemical oxidation (ISCO) has been deployed may contain binary mixtures of ground water contaminants and permanganate (MnO4-), an oxidant injected into the subsurface to destroy the contaminant. Commingling of the oxidant and ...

Graphene oxide/manganese ferrite nanohybrids for magnetic resonance imaging, photothermal therapy and drug delivery.

PubMed

Yang, Yan; Shi, Haili; Wang, Yapei; Shi, Benzhao; Guo, Linlin; Wu, Dongmei; Yang, Shiping; Wu, Huixia

2016-01-01

Superparamagnetic manganese ferrite (MnFe2O4) nanoparticles have been deposited on graphene oxide (GO) by the thermal decomposition of manganese (II) acetylacetonate and iron (III) acetylacetonate precursors in triethylene glycol. The resulting GO/MnFe2O4 nanohybrids show very low cytotoxicity, negligible hemolytic activity, and imperceptible in vivo toxicity. In vitro and in vivo magnetic resonance imaging experiments demonstrate that GO/MnFe2O4 nanohybrids could be used as an effective T2 contrast agent. The strong optical absorbance in the near-infrared (NIR) region and good photothermal stability of GO/MnFe2O4 nanohybrids result in the highly efficient photothermal ablation of cancer cells. GO/MnFe2O4 nanohybrids can be further loaded with doxorubicin (DOX) by π-π conjugate effect for chemotherapy. DOX release from GO/MnFe2O4 is significantly influenced by pH and can be triggered by NIR laser. The enhanced cancer cell killing by GO/MnFe2O4/DOX composites has been achieved when irradiated with near-infrared light, suggesting that the nanohybrids could deliver both DOX chemotherapy and photothermal therapy with a synergistic effect. © The Author(s) 2015.

Electromagnetic characteristics of manganese oxide-coated Fe3O4 nanoparticles at 2-18 GHz

NASA Astrophysics Data System (ADS)

Yang, R. B.; Liang, W. F.; Lin, C. K.

2011-04-01

The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the transmission/reflection method in 2-18 GHz. MnOx-coated Fe3O4 NPs were prepared by sol-gel method followed by heat-treating at 300, 400, and 500 °C, respectively. The heat-treated powders were then used as magnetic fillers and added to an epoxy resin to prepare MnOx-coated Fe3O4 composites for the complex permittivity (ɛ'-jɛ″) and permeability (μ'-jμ″) measurements. After the sol-gel process, the coating of manganese oxide (mixture of major Mn2O3 and minor Mn3O4) reduced the value of ɛ'. The lower the heat-treating temperature, the larger the decrease in ɛ'. The relative decrease in ɛ', compared with uncoated Fe3O4 nanoparticles, is 28.7, 23.5, and 20.0% for coated MnOx heat-treated at 300, 400, and 500 °C, respectively, while the relative decrease in ɛ″ is 74.1, 68.8, and 65.2%, respectively. In the present study, MnOx-coated Fe3O4 exhibited a significant decrease in dielectric loss tangent of ˜100% compared to that of uncoated NPs and can be of practical use for microwave components.

Ultrasmall PdmMn1-mOx binary alloyed nanoparticles on graphene catalysts for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Ahmed, Mohammad Shamsuddin; Park, Dongchul; Jeon, Seungwon

2016-03-01

A rare combination of graphene (G)-supported palladium and manganese in mixed-oxides binary alloyed catalysts (BACs) have been synthesized with the addition of Pd and Mn metals in various ratios (G/PdmMn1-mOx) through a facile wet-chemical method and employed as an efficient anode catalyst for ethanol oxidation reaction (EOR) in alkaline fuel cells. The as prepared G/PdmMn1-mOx BACs have been characterized by several instrumental techniques; the transmission electron microscopy images show that the ultrafine alloyed nanoparticles (NPs) are excellently monodispersed onto the G. The Pd and Mn in G/PdmMn1-mOx BACs have been alloyed homogeneously, and Mn presents in mixed-oxidized form that resulted by X-ray diffraction. The electrochemical performances, kinetics and stability of these catalysts toward EOR have been evaluated using cyclic voltammetry in 1 M KOH electrolyte. Among all G/PdmMn1-mOx BACs, the G/Pd0.5Mn0.5Ox catalyst has shown much superior mass activity and incredible stability than that of pure Pd catalysts (G/Pd1Mn0Ox, Pd/C and Pt/C). The well dispersion, ultrafine size of NPs and higher degree of alloying are the key factor for enhanced and stable EOR electrocatalysis on G/Pd0.5Mn0.5Ox.

Vaporization thermodynamic studies by high-temperature mass spectrometry on some three-phase regions over the MnO-TeO2 binary line in the Mn-Te-O ternary system.

PubMed

Narasimhan, T S Lakshmi; Sai Baba, M; Viswanathan, R

2006-12-28

Knudsen effusion mass spectrometric measurements have been performed in the temperature range of 850-950 K over four three-phase mixtures, each phase mixture having at least one phase lying on the MnO-TeO2 binary line of the Mn-Te-O phase diagram, and the rest of the phases lying above this binary line. The three-phase mixtures investigated are Mn3O4 + MnO + Mn6Te5O16; Mn3O4 + Mn6Te5O16 + MnTeO3; Mn3O4 + Mn3TeO6 + MnTeO3; and Mn3TeO6 + MnTeO3 + Mn2Te3O8. The vapor pressures of the gaseous species TeO2, TeO, and Te2 over these three-phase mixtures were measured, and various heterogeneous solid-gas reactions were evaluated along with the homogeneous gas-phase reaction TeO2(g) + 0.5Te2(g) = 2 TeO(g). The enthalpy and Gibbs free energy of formation of the four ternary Mn-Te-O phases were deduced at T = 900 K. These values (in kJ.mol-1), along with the estimated uncertainties in them are Delta(f)H(o)m = 4150 +/- 19, 752 +/- 11, 1710 +/- 11, 1924 +/- 40, and Delta(f)G(o)m= 2835 +/- 28, 511 +/- 11, 1254 +/- 19, 1238 +/- 38, for Mn6Te5O16, MnTeO3, Mn3TeO6, and Mn2Te3O8, respectively. A thermochemical assessment was made to examine the conditions under which the ternary Mn-Te-O phases could be formed on a stainless steel clad of mixed-oxide-fueled (MO2; M = U + Pu) fast breeder nuclear reactors. The phase Mn3TeO6 could be formed when the fuel is even slightly hyperstoichiometric (O/M = 2.0002) and the phase Mn6Te5O16 could also be formed when O/M = 2.0004. The threshold tellurium potential for the formation of Mn3TeO6 is higher than that for MnTe0.80 and CrTe1.10, but is comparable to that for MoTe1.10, and even lower than that for FeTe0.81 or NiTe0.63.

Platinum group elements and gold in ferromanganese crusts from Afanasiy-Nikitin seamount, equatorial Indian Ocean: Sources and fractionation

USGS Publications Warehouse

Banakar, V.K.; Hein, J.R.; Rajani, R.P.; Chodankar, A.R.

2007-01-01

The major element relationships in ferromanganese (Fe-Mn) crusts from Afanasiy-Nikitin seamount (ANS), eastern equatorial Indian Ocean, appear to be atypical. High positive correlations (r = 0.99) between Mn/Co and Fe/Co ratios, and lack of correlation of those ratios with Co, Ce, and Ce/Co, indicate that the ANS Fe-Mn crusts are distinct from Pacific seamount Fe-Mn crusts, and reflect region-specific chemical characteristics. The platinum group elements (PGE: Ir, Ru, Rh, Pt, and Pd) and Au in ANS Fe-Mn crusts are derived from seawater and are mainly of terrestrial origin, with a minor cosmogenic component. The Ru/Rh (0.5-2) and Pt/Ru ratios (7-28) are closely comparable to ratios in continental basalts, whereas Pd/Ir ratios exhibit values ( 0.75) correlations between water depth and Mn/Co, Fe/Co, Ce/Co, Co, and the PGEs. Fractionation of the PGE-Au from seawater during colloidal precipitation of the major-oxide phases is indicated by well-defined linear positive correlations (r > 0.8) of Co and Ce with Ir, Ru, Rh, and Pt; Au/Co with Mn/Co; and by weak or no correlations of Pd with water depth, Co-normalized major-element ratios, and with the other PGE (r < 0.5). The strong enrichment of Pt (up to 1 ppm) relative to the other PGE and its positive correlations with Ce and Co demonstrate a common link for the high concentrations of all three elements, which likely involves an oxidation reaction on the Mn-oxide and Fe-oxyhydroxide surfaces. The documented fractionation of PGE-Au and their positive association with redox sensitive Co and Ce may have applications in reconstructing past-ocean redox conditions and water masses.

Magnetic and crystallographic properties of ZrM 2-δZn 20+δ (M=Cr–Cu)

DOE PAGES

Svanidze, E.; II, M. Kindy; Georgen, C.; ...

2016-04-29

Single crystals of the cubic Laves ternaries ZrM 2-δZn 20+δ (M=Mn, Fe, Co, Ni and Cu, 0 ≤ δ ≤ 1) have been synthesized in this paper using a self-flux method. The magnetic properties of these compounds were compared with structurally similar cubic binaries ZrM 2 (M=Mn, Fe, Co, Ni and Cu). A transition from local to itinerant moment magnetism was observed for M=Fe and M=Mn, while all other ternaries exhibit weakly para- or diamagnetic behavior. The local-to-itinerant crossover can be explained by a nearly two-fold increase of the M–M bond length d M–M in ZrM 2-δZn 20+δ compounds, asmore » compared with the ZrM 2 binaries. Additionally, we report two new compounds in this series ZrCrZn 21 and ZrCu 2Zn 20. Finally, analysis of crystallographic and magnetic trends in these materials will aid in understanding of magnetism in general and 3d intermetallics in particular.« less

Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

NASA Astrophysics Data System (ADS)

Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

2012-12-01

The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic to anoxic conditions at Hot Spring, contemporaneous to an Oceanic Anoxic Event. The similarity of the Nd isotopic signal of the carbonate matrix of foraminifera with that of fish teeth suggests that it records the Nd isotope composition of bottom shelf seawater as well. Inferred bottom shelf water Nd isotope compositions at Hot Spring are quite radiogenic, between -7 and -6 ɛ-units, about 2.5-4 ɛ-units higher than that of the contemporaneous local detrital fraction. In contrast, in both sections Fe-Mn oxides leached directly from the decarbonated sediment tend to yield a less radiogenic Nd isotopic composition, typically between 0.2 and 0.8 ɛ-units lower, that is intermediate between that of fish teeth and of the detrital fraction. This suggests the contribution of pre-formed continental Fe-Mn oxides to the Nd isotopic signal, along with authigenic marine oxides, or a detrital contamination during leaching.

Magnetoresistance enhancement in specular, bottom-pinned, Mn83Ir17 spin valves with nano-oxide layers

NASA Astrophysics Data System (ADS)

Veloso, A.; Freitas, P. P.; Wei, P.; Barradas, N. P.; Soares, J. C.; Almeida, B.; Sousa, J. B.

2000-08-01

Bottom-pinned Mn83Ir17 spin valves with enhanced specular scattering were fabricated, showing magnetoresistance (MR) values up to 13.6%, lower sheet resistance R□ and higher ΔR□. Two nano-oxide layers (NOL) are grown on both sides of the CoFe/Cu/CoFe spin valve structure by natural oxidation or remote plasma oxidation of the starting CoFe layer. Maximum MR enhancement is obtained after just 1 min plasma oxidation. Rutherford backscattering analysis shows that a 15±2 Å oxide layer grows at the expense of the initial (prior to oxidation) CoFe layer, with ˜12% reduction of the initial 40 Å CoFe thickness. X-ray reflectometry indicates that Kiessig fringes become better defined after NOL growth, indicating smoother inner interfaces, in agreement with the observed decrease of the spin valve ferromagnetic Néel coupling.

Ferromanganese deposits from the Gulf of Alaska seamount province: mineralogy, chemistry, and origin.

USGS Publications Warehouse

Koski, R.A.

1988-01-01

Petrographic and chemical data presented and discussed permit the following conclusions regarding the high-latitude Gulf of Alaska (GA) Fe-Mn deposits: 1) thick (10-50 mm) Fe-Mn crusts form on alkali-basalt and volcaniclastic substrates by hydrogenetic processes, contain delta -MnO2 as the principal Mn phase, and have compositions similar to those of seamount crusts from comparable depths in the Hawaiian archipelago. GA crusts have higher Mn/Fe and lower Co contents than crusts from low-altitude, central Pacific seamounts; 2) thin (<10 mm) crusts on tuffaceous conglomerate, sandstone and phosphorite have a high proportion of crystalline Mn oxides and are genetically related to vein deposits; 3) vein deposits of todorokite and cryptomelane form during low-T oxidative diagenesis of volcanogenic sediment. Mn and other transition metals are supplied during the initial palagonitization of basaltic glass. The oxidation of Fe2+ to Fe3+ in palagonite and the dissolution of the diluted microfossil fraction of the sediment lower the Eh of the ambient pore fluid and enhance the solubility of Mn2+. The K released during the formation of palagonite may be redeposited in secondary phyllosilicate minerals, phillipsite, todorokite and cryptomelane; 4) the vein deposits formed soon after the deposition of sediment derived from the erosion and mass wasting of Mill Seamount but before crust deposition. Therefore, the deposition of hydrogenous crusts and the deposition of diagenetic veins are chemically distinct processes in time and space.-J.M.H.

Metal dynamics in Lake Vanda (Wright Valley, Antarctica)

NASA Technical Reports Server (NTRS)

Green, W. J.; Ferdelman, T. G.; Canfield, D. E.; DeVincenzi, D. L. (Principal Investigator)

1989-01-01

Data are reported for Mn, Fe, Co, Ni, Cu and Cd in the Onyx River, and for Mn, Co, Ni, Cu and Cd in Lake Vanda, a closed-basin Antarctic lake. Oxic water concentrations for Co, Ni, Cu and Cd were quite low and approximate pelagic ocean values. Scavenging of these metals by sinking particles is strongly indicated. Deep-lake profiles reveal a sharp peak in the concentrations of Mn, Fe and Co at the oxic-anoxic boundary at 60 m. Maxima for Ni, Cu and Cd occur higher in the water column, in the vicinity of a Mn submaximum, suggesting early release of these metals from sinking manganese oxide-coated particles. A rough steady-state model leads to the conclusion that there is a large downward flux of Mn into the deep lake and that this flux is sufficient to explain the annual loss of Co, Ni, Cu and Cd. A pronounced geochemical separation between Fe and Mn apparently occurs in this system--Fe being best lost in near-shore environments and Mn being lost in deeper waters. Comparison of metal residence times in Lake Vanda with those in the oceans shows that in both systems Mn, Fe and Co are much more reactive than Ni, Cu and Cd. Energetically favorable inclusion of the more highly charged metals, Mn(IV), Fe(III) and Co(III), into oxide-based lattices is a plausible explanation.

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

USGS Publications Warehouse

Hein, J.R.; Koschinsky, A.; Halliday, A.N.

2003-01-01

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth's crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth's crustal mean of about 1 ppb, compared with 250 times for the next most enriched element. We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases. Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO2, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ???10% is leached with the MnO2. Thermodynamic calculations indicate that Te occurs predominantly as H5TeO6- in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO2 in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce. ?? 2003 Elsevier Science Ltd.

Biogeochemistry of manganese in ferruginous Lake Matano, Indonesia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, C.; Crowe, S.A.; Sturm, A.

2012-12-13

This study explores Mn biogeochemistry in a stratified, ferruginous lake, a modern analogue to ferruginous oceans. Intense Mn cycling occurs in the chemocline where Mn is recycled at least 15 times before sedimentation. The product of biologically catalyzed Mn oxidation in Lake Matano is birnessite. Although there is evidence for abiotic Mn reduction with Fe(II), Mn reduction likely occurs through a variety of pathways. The flux of Fe(II) is insufficient to balance the reduction of Mn at 125m depth in the water column, and Mn reduction could be a significant contributor to CH{sub 4} oxidation. By combining results from synchrotron-basedmore » X-ray fluorescence and X-ray spectroscopy, extractions of sinking particles, and reaction transport modeling, we find the kinetics of Mn reduction in the lake's reducing waters are sufficiently rapid to preclude the deposition of Mn oxides from the water column to the sediments underlying ferruginous water. This has strong implications for the interpretation of the sedimentary Mn record.« less

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE PAGES

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia; ...

2017-10-31

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Shiva; Zhao, Shuai; Wang, Xiao Xia

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substratemore » with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.« less

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis.

PubMed

Wang, He; Jia, Yongfeng; Wang, Shaofeng; Zhu, Huijie; Wu, Xing

2009-08-15

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH)(3)>Al(2)O(3)>Fe(3)O(4)>MnO(2)>FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH)(3)>Fe(3)O(4)>Al(2)O(3)>FeOOH>MnO(2), while by citric acid: Al(OH)(3)> or =Al(2)O(3)>Fe(3)O(4)>FeOOH>MnO(2). This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH)(3) was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO(2) adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

Synthesis of KMnO4-treated magnetic graphene oxide nanocomposite (Fe3O4@GO/MnO x ) and its application for removing of Cu2+ ions from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Huining; Chang, Qing; Jiang, Yu; Li, Huili; Yang, Yahong

2018-04-01

A magnetic KMnO4-treated graphene-oxide-based nanocomposite, Fe3O4@GO/MnO x , was synthesized through a facile hydrothermal technique. The properties of the Fe3O4@GO/MnO x nanocomposite were characterized by SEM, XRD and FTIR. Batch experiments showed that the maximum adsorption capacity calculated by the Langmuir model for Cu2+ was 62.65 mg g-1 at T = 303.15 K. Kinetics and XPS analysis also revealed that the mechanism of Cu2+ removal was mainly a chemical adsorption process involving both the MnO x particles and oxygen functional groups. The prepared Fe3O4@GO/MnO x was found to be an ideal adsorbent for the removal of Cu2+ ions due to the MnO x particle coating, and was easily separated using a magnetic field after utilization. Reusability studies imply that Fe3O4@GO/MnO x is a suitable material for heavy metal ion removal from aqueous solutions in real applications.

Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

PubMed Central

Thamdrup, Bo; Rosselló-Mora, Ramón; Amann, Rudolf

2000-01-01

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (Corg) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ∼1 cm, while SO42− reduction accounted for the entire Corg oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of Corg oxidation rates. The relative contribution of Mn reduction to Corg oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 105 cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm−3, while counts of Fe reducers were <102 cm−3. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ∼10 μmol cm−3 and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche. PMID:10877783

Influence of nano-oxide layers on IrMn pinned bottom spin-valves at different positions

NASA Astrophysics Data System (ADS)

Qiu, J. J.; Li, K. B.; Luo, P.; Zheng, Y. K.; Wu, Y. H.

2004-05-01

The influence of nano-oxide layer (NOL) inserted at different positions on interlayer coupling (Hin), coercivity of free layer (Hcf), exchange bias (Hex) and MR ratio of IrMn pinned bottom type spin-valves (SV) were studied. Weak antiferromagnetic interlayer coupling was observed in NOL-added SV. The NOL inside pinned layer and after free layer can enhance the MR ratio remarkably. MR of SV with a structure Ta3/NiFe2/IrMn6/CoFe1/NOL/CoFe2.3/Cu2.2/CoFe2.3/AlO reached 18.2%. This is one of the best values ever reported for all-metal single spin-valves.

Production of Biogenic Mn Oxides by Leptothrix discophora SS-1 in a Chemically Defined Growth Medium and Evaluation of Their Pb Adsorption Characteristics

PubMed Central

Nelson, Yarrow M.; Lion, Leonard W.; Ghiorse, William C.; Shuler, Michael L.

1999-01-01

Biogenic Mn oxides were produced by the bacterium Leptothrix discophora SS-1 (= ATCC 3182) in a chemically defined mineral salts medium, and the Pb binding and specific surface area of these oxides were characterized. Growth of SS-1 in the defined medium with pyruvate as a carbon and energy source required the addition of vitamin B12. Complete oxidation of Mn(II) within 60 h required the addition of ≥0.1 μM FeSO4. Pb adsorption isotherms were determined for the biogenic Mn oxides (and associated cells with their extracellular polymer) and compared to the Pb adsorption isotherms of cells and exopolymer alone, as well as to abiotic Mn oxides. The Pb adsorption to cells and exopolymer with biogenic Mn oxides (0.8 mmol of Mn per g) at pH 6.0 and 25°C was 2 orders of magnitude greater than the Pb adsorption to cells and exopolymer alone (on a dry weight basis). The Pb adsorption to the biogenic Mn oxide was two to five times greater than the Pb adsorption to a chemically precipitated abiotic Mn oxide and several orders of magnitude greater than the Pb adsorption to two commercially available crystalline MnO2 minerals. The N2 Brunauer-Emmet-Teller specific surface areas of the biogenic Mn oxide and fresh Mn oxide precipitate (224 and 58 m2/g, respectively) were significantly greater than those of the commercial Mn oxide minerals (0.048 and 4.7 m2/g). The Pb adsorption capacity of the biogenic Mn oxide also exceeded that of a chemically precipitated colloidal hydrous Fe oxide under similar solution conditions. These results show that amorphous biogenic Mn oxides similar to those produced by SS-1 may play a significant role in the control of trace metal phase distribution in aquatic systems. PMID:9872777

Transition metal redox and Mn disproportional reaction in LiMn0.5Fe0.5PO4 electrodes cycled with aqueous electrolyte

NASA Astrophysics Data System (ADS)

Zhuo, Zengqing; Hu, Jiangtao; Duan, Yandong; Yang, Wanli; Pan, Feng

2016-07-01

We performed soft x-ray absorption spectroscopy (sXAS) and a quantitative analysis of the transition metal redox in the LiMn0.5Fe0.5PO4 electrodes upon electrochemical cycling. In order to circumvent the complication of the surface reactions with organic electrolyte at high potential, the LiMn0.5Fe0.5PO4 electrodes are cycled with aqueous electrolyte. The analysis of the transitional metal L-edge spectra allows a quantitative determination of the redox evolution of Mn and Fe during the electrochemical cycling. The sXAS analysis reveals the evolving Mn oxidation states in LiMn0.5Fe0.5PO4. We found that electrochemically inactive Mn2+ is formed on the electrode surface during cycling. Additionally, the signal indicates about 20% concentration of Mn4+ at the charged state, providing a strong experimental evidence of the disproportional reaction of Mn3+ to Mn2+ and Mn4+ on the surface of the charged LiMn0.5Fe0.5PO4 electrodes.

Biquadratic coupling through nano-oxide layers in pinned layers of IrMn-based spin valves

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Lu, K. H.

2003-05-01

We have investigated the coupling between top and bottom pinned layers through various nano-oxide layers (NOLs) in IrMn-based spin valves. The NOLs were formed by using oxygen-plasma oxidation or natural oxidation on 1 nm metallic layers. By inserting naturally oxidized Co-NOLs in the pinned layer, strong ferromagnetic coupling through NOLs and high specularity at the NOL interface were achieved. In contrast, when the plasma-oxidized Co-NOLs were inserted, ferromagnetic coupling through NOLs disappeared, plausibly due to the formation of nonferromagnetic oxides, which led to a low magnetoresistance (MR). Insertion of naturally oxidized Ni80Fe20-NOLs showed the same results as that of naturally oxidized Co-NOLs. On the other hand, biquadratic coupling between top and bottom pinned-Co90Fe10 layers was observed by inserting plasma-oxidized Ni80Fe20-NOLs. The highest MR was obtained when the field was applied along the direction perpendicular to the field-annealing direction. Similar biquadratic coupling was also found with naturally oxidized or plasma-oxidized Fe-NOLs. We suggest that the biquadratic coupling between pinned Co90Fe10 layers through NOLs results from the coupling between Fe (or Co90Fe10) and Fe+3 oxides

Formation of (FexMn(2-x))O3 solid solution and high sulfur capacity properties of Mn-based/M41 sorbents for hot coal gas desulfurization.

PubMed

Zhang, Y; Liu, B S; Zhang, F M; Zhang, Z F

2013-03-15

Several MCM-41 materials were synthesized at different conditions by hydrothermal procedure using cheap and easily available industrial water glass as silica source. Fe doped manganese-based oxide/MCM-41 sorbents were prepared by a sol-gel method. The effects of loadings of metal oxide, Fe/Mn molar ratios over MCM-41 and reaction temperature on the performance of sorbent for hot coal gas desulfurization were investigated. Various techniques such as BET, XRD, XPS, LRS and HRTEM were used to characterize the sorbents. The result indicated Fe(3+) ions could occupy a position of Mn(3+) in cubic lattice of Mn2O3 and the (FexMn2-x)O3 solid solution is mainly active phase of sorbent. Moreover, the result of nine successive sulfurization-regeneration cycles of sorbent showed high sulfur adsorption capacity and endurable stability of FeMn4Ox/MCM-41 for H2S removal. Copyright © 2013 Elsevier B.V. All rights reserved.

Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic

NASA Astrophysics Data System (ADS)

Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.

2017-12-01

Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.

Semiconductor Ceramic Mn0.5Fe1.5O3-Fe2O3 from Natural Minerals as Ethanol Gas Sensors

NASA Astrophysics Data System (ADS)

Aliah, H.; Syarif, D. G.; Iman, R. N.; Sawitri, A.; Sanjaya WS, M.; Nurul Subkhi, M.; Pitriana, P.

2018-05-01

In this research, Mn and Fe-based ceramic gas sensing were fabricated and characterized. This research used natural mineral which is widely available in Indonesia and intended to observe the characteristics of Mn and Fe-based semiconducting material. Fabricating process of the thick films started by synthesizing the ceramic powder of Fe(OH)3 and Mn oxide material using the precipitation method. The deposition from precipitation method previously was calcined at a temperature of 800 °C to produce nanoparticle powder. Nanoparticle powder that contains Mn and Fe oxide was mixed with an organic vehicle (OV) to produce a paste. Then, the paste was layered on the alumina substrate by using the screen printing method. XRD method was utilized to characterize the thick film crystal structure that has been produced. XRD spectra showed that the ceramic layer was formed from the solid Mn0.5Fe1.5O3 (bixbyite) and Fe2O3. In addition, the electrical properties (resistance) examination was held in the room that contains air and ethanol to determine the sensor sensitivity of ethanol gas. The sensor resistance decreases as the ethanol gas was added, showing that the sensor was sensitive to ethanol gas and an n-type semiconductor. Gas sensor exhibit sensitive characterization of ethanol gas on the concentration of (100 to 300) ppm at a temperature of (150 to 200) °C. This showed that the Mn0.5Fe1.5O3-Fe2O3 ceramic semiconductor could be utilized as the ethanol gas detector.

Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

PubMed Central

Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

2013-01-01

For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects

NASA Astrophysics Data System (ADS)

Talic, Belma; Molin, Sebastian; Wiik, Kjell; Hendriksen, Peter Vang; Lein, Hilde Lea

2017-12-01

MnCo2O4, MnCo1.7Cu0.3O4 and MnCo1.7Fe0.3O4 are investigated as coatings for corrosion protection of metallic interconnects in solid oxide fuel cell stacks. Electrophoretic deposition is used to deposit the coatings on Crofer 22 APU alloy. All three coating materials reduce the parabolic oxidation rate in air at 900 °C and 800 °C. At 700 °C there is no significant difference in oxidation rate between coated samples and uncoated pre-oxidized Crofer 22 APU. The cross-scale area specific resistance (ASR) is measured in air at 800 °C using La0.85Sr0.1Mn1.1O3 (LSM) contact plates to simulate the interaction with the cathode in a SOFC stack. All coated samples have three times lower ASR than uncoated Crofer 22 APU after 4370 h aging. The ASR increase with time is lowest with the MnCo2O4 coating, followed by the MnCo1.7Fe0.3O4 and MnCo1.7Cu0.3O4 coatings. LSM plates contacted to uncoated Crofer 22 APU contain significant amounts of Cr after aging, while all three coatings effectively prevent Cr diffusion into the LSM. A complex Cr-rich reaction layer develops at the coating-alloy interface during oxidation. Cu and Fe doping reduce the extent of this reaction layer at 900 °C, while at 800 °C the effect of doping is insignificant.

Chemical composition of individual aerosol particles in workplace air during production of manganese alloys.

PubMed

Gunst, S; Weinbruch, S; Wentzel, M; Ortner, H M; Skogstad, A; Hetland, S; Thomassen, Y

2000-02-01

Aerosol particle samples were collected at ELKEM ASA ferromanganese (FeMn) and silicomanganese (SiMn) smelters at Porsgrunn, Norway, during different production steps: raw material mixing, welding of protective steel casings, tapping of FeMn and slag, crane operation moving the ladles with molten metal, operation of the Metal Oxygen Refinement (MOR) reactor and casting of SiMn. Aerosol fractions were assessed for the analysis of the bulk elemental composition as well as for individual particle analysis. The bulk elemental composition was determined by inductively coupled plasma atomic emission spectrometry. For individual particle analysis, an electron microprobe was used in combination with wavelength-dispersive techniques. Most particles show a complex composition and cannot be attributed to a single phase. Therefore, the particles were divided into six groups according to their chemical composition: Group I, particles containing mainly metallic Fe and/or Mn; Group II, slag particles containing mainly Fe and/or Mn oxides; Group III, slag particles consisting predominantly of oxidized flux components such as Si, Al, Mg, Ca, Na and K; Group IV, particles consisting mainly of carbon; Group V, mixtures of particles from Groups II, III and IV; Group VI, mixtures of particles from Groups II and III. In raw material mixing, particles originating from the Mn ores were mostly found. In the welding of steel casings, most particles were assigned to Group II, Mn and Fe oxides. During the tapping of slag and metal, mostly slag particles from Group III were found (oxides of the flux components). During movement of the ladles, most particles came from Group II. At the MOR reactor, most of the particles belonged to the slag phase consisting of the flux components (Group III). The particles collected during the casting of SiMn were mainly attributed to the slag phase (Groups III and V). Due to the compositional complexity of the particles, toxicological investigations on the kinetics of pure compounds may not be easily associated with the results of this study.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

Development of a reactive zone technology for simultaneous in situ immobilisation of radium and uranium

NASA Astrophysics Data System (ADS)

Burghardt, D.; Kassahun, A.

2005-12-01

Simultaneous in situ immobilisation of uranium (U) and radium (226Ra) by injectible amounts of grey cast iron (gcFe), nano-scale iron (naFe) and a gcFe/MnO2 mixture (1:1) was studied in batch and column tests. Both 0.5 g/L naFe and gcFe are effective in 226Ra and U removal from mine water, whereas MnO2 addition clearly increased the efficiency of gcFe for 226Ra and U immobilisation. In a column test with 0.6 wt% gcFe/MnO2 mixture (1:1), neither 226Ra nor U was detected in the effluent after replacement of 45 pore volumes. A sequential extraction under flow condition revealed 226Ra to be mostly occluded in manganese oxides. Uranium was mostly sorbed onto poorly crystalline iron hydroxides, but a significant part was found to be occluded in manganese oxides also. The results of this study suggest that MnO2 promotes iron hydroxide formation under slightly reducing environmental conditions resulting in an increased pollutant retention capacity.

Non-Metallic Ti Oxides and MnS/FeS2 Complex Precipitation in Ti-Killed Steel

NASA Astrophysics Data System (ADS)

Chen, Jieyun; Zhao, Dan; Li, Huigai; Zheng, Shaobo

Titanium deoxidized experiments can be carried in vacuum induction furnace by adding Ti-Fe alloy in molten steel to simulate strip casting. Sub-rapid solidification samples were obtained in the method of suing copper mold. The morphology, the chemical composition and the structures of nanometer precipitations were carried out to investigate by transmission electron microscope (TEM) with Energy Dispersive X ray Spectrum (EDX) and by collecting diffraction patterns with carbon extraction specimens. It has been found that titanium oxides were TiO monoclinic, Ti4O7 anorthic and TiO2 orthogonal structure in one nanometer inclusion, as the composite oxide was precipitated MnS/FeS2 cubic structure during sub-rapid solidification. Thermodynamic calculation analysis showed that it was possible to precipitate different kinds of nonstoichiometric TiOx. The solid solution between MnS/FeS2 will precipitate on the surface of titanium oxides because of good coherency relationship.

Elevated Temperature Deformation of Fe-39.8Al and Fe-15.6Mn-39.4Al

NASA Technical Reports Server (NTRS)

Whittenberger, J. Daniel

2004-01-01

The elevated temperature compressive properties of binary Fe-39.8 at % Al and Fe-15.6Mn-39.4Al have been measured between 1000 and 1300 K at strain rates between 10(exp 7) and 10(exp 3)/ s. Although the Mn addition to iron aluminide did not change the basic deformation characteristics, the Mn-modified alloy was slightly weaker. In the regime where deformation of FeAl occurs by a high stress exponent mechanism (n = 6), strength increases as the grain size decreases at least for diameters between approx. 200 and approx. 10 microns. Due to the limitation in the grain size-flow stress-temperature-strain rate database, the influence of further reductions of the grain size on strength is uncertain. Based on the appearance of subgrains in deformed iron aluminide, the comparison of grain diameters to expected subgrain sizes, and the grain size exponent and stress exponent calculated from deformation experiments, it is believed that grain size strengthening is the result of an artificial limitation on subgrain size as proposed by Sherby, Klundt and Miller.

Neurotoxic effects of subchronic intratracheal Mn nanoparticle exposure alone and in combination with other welding fume metals in rats.

PubMed

Máté, Zsuzsanna; Horváth, Edina; Papp, András; Kovács, Krisztina; Tombácz, Etelka; Nesztor, Dániel; Szabó, Tamás; Szabó, Andrea; Paulik, Edit

2017-04-01

Manganese (Mn) is a toxic heavy metal exposing workers in various occupational settings and causing, among others, nervous system damage. Metal fumes of welding, a typical source of Mn exposure, contain a complex mixture of metal oxides partly in nanoparticle form. As toxic effects of complex substances cannot be sufficiently understood by examining its components separately, general toxicity and functional neurotoxicity of a main pathogenic welding fume metal, Mn, was examined alone and combined with iron (Fe) and chromium (Cr), also frequently found in fumes. Oxide nanoparticles of Mn, Mn + Fe, Mn + Cr and the triple combination were applied, in aqueous suspension, to the trachea of young adult Wistar rats for 4 weeks. The decrease of body weight gain during treatment, caused by Mn, was counteracted by Fe, but not Cr. At the end of treatment, spontaneous and evoked cortical electrical activity was recorded. Mn caused a shift to higher frequencies, and lengthened evoked potential latency, which were also strongly diminished by co-application of Fe only. The interaction of the metals seen in body weight gain and cortical activity were not related to the measured blood and brain metal levels. Fe might have initiated protective, e.g. antioxidant, mechanisms with a more general effect.

Genetic and biochemical effects induced by iron ore, Fe and Mn exposure in tadpoles of the bullfrog Lithobates catesbeianus.

PubMed

Veronez, Alexandra Caroline da Silva; Salla, Rômulo Victor; Baroni, Vinícius Dadalto; Barcarolli, Indianara Fernanda; Bianchini, Adalto; Dos Reis Martinez, Claudia Bueno; Chippari-Gomes, Adriana Regina

2016-05-01

For decades, the extraction of minerals has intensified in order to meet the demand of industry. Iron ore deposits are important sources of metals, such as iron (Fe) and manganese (Mn). The particulate ores can be dispersed during extraction, transport and storage, with potential to induce biological impacts. Amphibians are very sensitive to environmental stressors. Therefore, the present study aimed to assess the effects of iron ore, Fe and Mn exposure during the metamorphosis of Lithobates catesbeianus. Endpoints analyzed included morphological (biometrical and developmental analyses), whole body Fe and Mn concentration in, plasma ferritin concentration, erythrocyte DNA damage (measured through comet assay and micronucleus test) and liver activity of enzymes involved in oxidative status [glutathione S-transferase (GST) and catalase (CAT)]. Tadpoles were kept under control condition (no contaminant addition) or exposed to iron ore (3.79mg/L as fine particulate matter); Fe (nominal concentration: 0.51mg/L Fe as C10H12FeN2NaO8; Fe-EDTA); and Mn (nominal concentration: 5.23mg/L Mn as 4H2O.MnCl2) for 30 days. Virtually, no mortality was observed, except for one tadpole found dead in the iron ore treatment. However, tadpoles exposed to iron ore had longer tail than those kept under control conditions while tadpoles exposed to manganese chloride showed higher body length than control ones. Exposure to Fe and Mn induced a delay in tadpole metamorphosis, especially when these metals are presented not as a mixture (iron ore). Tadpoles exposed to iron ore had increased whole body Fe and Mn while those exposed to Fe and Mn accumulated each metal individually. Tadpoles exposed to any of the contaminants tested showed a significant increase in erythrocyte DNA damage and frequency of micronuclei. In addition, they showed higher liver GST activity respect with those kept under control conditions. Plasma ferritin concentration and liver CAT activity were higher only in tadpoles exposed to iron ore. These findings indicated that tadpoles accumulated Fe and Mn at the whole body level after exposure to the single metals or to their mixture as iron ore. In addition, they indicate that Fe and Mn accumulation can induce oxidative stress with consequent significant developmental, genotoxic and biochemical effects in L. catesbeianus tadpoles. Copyright © 2016 Elsevier B.V. All rights reserved.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Speciation of Energy Critical Elements in Marine Ferromanganese Crusts and Nodules by Principal Component Analysis and Least-squares fits to XAFS Spectra

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.

Magnetic properties of doped Mn-Ga alloys made by mechanical milling and heat treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Daniel R.; National High Magnetic Field Laboratory, Tallahassee, FL 32310; Han, Ke

2016-05-15

Mn-Ga alloys have shown hard magnetic properties, even though these alloys contain no rare-earth metals. However, much work is needed before rare-earth magnets can be replaced. We have examined the magnetic properties of bulk alloys made with partial replacement of both the Mn and Ga elements in the Mn{sub 0.8}Ga{sub 0.2} system. Bulk samples of Mn-Ga-Bi, Mn-Ga-Al, Mn-Fe-Ga and Mn-(FeB)-Ga alloys were fabricated and studied using mechanically milling and heat treatments while altering the atomic percentage of the third element between 2.5 and 20 at%. The ternary alloy exhibits all hard magnetic properties at room temperature with large coercivity. Annealedmore » Mn-Ga-X bulk composites exhibit high coercivities up to 16.6 kOe and remanence up to 9.8 emu/g, that is increased by 115% over the binary system.« less

Dietary Manganese Modulates PCB126 Toxicity, Metal Status, and MnSOD in the Rat

PubMed Central

Wang, Bingxuan; Klaren, William D.; Wels, Brian R.; Simmons, Donald L.; Olivier, Alicia K.; Wang, Kai; Robertson, Larry W.; Ludewig, Gabriele

2016-01-01

PCB126 (3,3′,4,4′,5-pentachlorobiphenyl) is a potent aryl hydrocarbon receptor agonist and induces oxidative stress. Because liver manganese (Mn) levels decrease in response to PCB126, a Mn dietary study was designed to investigate the role of Mn in PCB126 toxicity. Male Sprague Dawley rats received diets containing 0, 10, or 150 ppm added Mn for 3 weeks, followed by a single ip injection of corn oil or PCB126 (5 µmol/kg body weight). After 2 weeks, Mn, Cu, Zn, and Fe levels in the heart, liver, and liver mitochondria, and Mn-containing superoxide dismutase (MnSOD) and metallothionein mRNA, MnSOD protein, and MnSOD activity were determined. Mn levels in liver, heart, and liver mitochondria were strongly decreased by the Mn-deficient diet. Small effects on Fe levels and a stepwise increase in MnSOD activity with dietary Mn were also visible. PCB126 caused profound changes in Cu (up), Zn, Fe, and Mn (down) in liver, but not in heart, and differing effects (Cu, Zn, and Fe up, Mn down) in liver mitochondria. Liver MnSOD and metallothionein mRNA levels and MnSOD protein were increased but MnSOD activity was decreased by PCB126. PCB126-induced liver enlargement was dose-dependently reduced with increasing dietary Mn. These changes in metals homeostasis and MnSOD activity in liver but not heart may be a/the mechanism of PCB126 liver-specific toxicity. Specifically, transport of Fenton metals (Cu, Fe) into and Mn out of the mitochondria, a probable mechanism for lower MnSOD activity, may be a/the cause of PCB126-induced oxidative stress. The role of metallothioneins needs further evaluation. Dietary Mn slightly alleviated PCB126-induced toxicities. PMID:26660635

Effects of Exogenous Gibberellic Acid3 on Iron and Manganese Plaque Amounts and Iron and Manganese Uptake in Rice

PubMed Central

Guo, Yue; Zhu, Changhua; Gan, Lijun; Ng, Denny; Xia, Kai

2015-01-01

Gibberellins (GA) regulate various components of plant development. Iron and Mn plaque result from oxiding and hydroxiding Fe and Mn, respectively, on the roots of aquatic plant species such as rice (Oryza sativa L.). In this study, we found that exogenous gibberellic acid3 (GA3) spray decreased Fe plaque, but increased Mn plaque, with applications of Kimura B nutrient solution. Similar effects from GA3, leading to reduced Fe plaque and increased Mn plaque, were also found by scanning electron microscopy and energy dispersive X-ray spectrometric microanalysis. Reduced Fe plaque was observed after applying GA3 to the groups containing added Fe2+ (17 and 42 mg•L-1) and an increasing trend was detected in Mn plaques of the Mn2+ (34 and 84 mg•L-1) added treatments. In contrast, an inhibitor of GA3, uniconazole, reversed the effects of GA3. The uptake of Fe or Mn in rice plants was enhanced after GA3 application and Fe or Mn plaque production. Strong synergetic effects of GA3 application on Fe plaque production were detected. However, no synergetic effects on Mn plaque production were detected. PMID:25710173

An integrated approach to asses origin and mobilization of As, Fe and Mn in groundwater: the case study of Cremona (northern Italy)

NASA Astrophysics Data System (ADS)

Rotiroti, Marco; Bonomi, Tullia; Fumagalli, Letizia

2013-04-01

The present work concerns the analysis of the hydrogeology and the hydrogeochemistry of the As, Fe, Mn rich groundwater of the alluvial multi-layer aquifer in the lower Po Plain of Cremona (northern Italy). In this analysis, an integrated approach is applied in order to understand the origins (natural or anthropic) and chemical mechanisms of high groundwater As, Fe and Mn concentrations found in the study area. The study area covers a 50 km2 wide area around the urban territory of Cremona. It is located near the confluence between Adda and Po rivers. The multi-aquifer system which interests the first 200-250 m of depth is investigated. The integrated approach involves the (a) collection of historical data related to water quality, water levels and well logs; (b) storage of collected data in specific databases and geographical information systems; (c) design and execution of two field surveys of water levels and water quality, realized in July 2010 and July 2012, concerning also groundwater sampling for isotope and microbiological analysis; (d) construction of a 3D model of aquifer hydrogeological properties (deposits texture, hydraulic conductivity and effective porosity), built by means of ordinary kriging interpolation of numerical values derived from the coding of well logs; (e) analysis of the hydrodynamic properties of the system on the basis of the field measurements; (f) analysis of water quality data (both field and historical data) considering the hydrogeological and hydrodynamic properties of the aquifer system; (g) analysis of isotope and microbiological measurements; (h) implementation of a 1D reactive transport model in order to better understand the hydrogeochemical mechanisms in the system; (i) elaboration of a general hydrogeochemical conceptual model concerning possible origins and chemical mechanisms for the high groundwater As, Fe, Mn and NH4 concentrations, considering also possible anthropogenic influences; (j) development of management tools, as natural background levels (NBL) derivation, supporting groundwater resources protection by public authorities. This approach allows to assume the process of natural organic matter degradation (i.e. peat) as primary control factor on high As, Fe, Mn and NH4 concentrations. Degradation of peat is associated with the consecutive reduction of O2, NO3-, Mn(IV), Fe(III), SO42-, CO2. The reductive dissolution of Mn and Fe oxides (contained in the aquifer sediments) leads to high concentrations of dissolved Fe and Mn, but also to high concentrations of dissolved As, which is generally sorbed on Mn and Fe oxides. Dissolved As concentration can be also lowered by different processes (co-precipitation of As in iron sulfides, precipitation of arsenic sulfides, sorption of As on the remaining Fe-oxides and Mn-oxides, etc.). NH4 is released from the degradation of organic nitrogen of peat. Therefore, a natural origin of As, Fe, Mn and NH4 can be assumed. In addiction, anthropogenic influences on groundwater As, Fe, Mn and NH4 concentrations are locally identified in two sites located in the study area, that are affected by hydrocarbons and organic leachate pollution.

The Energetics of Oxide Multilayer Systems: SOFC Cathode and Electrolyte Materials

NASA Astrophysics Data System (ADS)

Kemik, Nihan

Complex oxides are evoking a surge of scientific and technological interest due to the unexpected properties of their interfaces which have been shown to differ from the constituent materials. Layered oxide structures have found wide use in applications ranging from electronic and magnetic devices to solid oxide fuel cells (SOFCs). For devices such as SOFCs which utilize multilayers at elevated temperatures, it is critical to know the relative stabilities of these interfaces since they directly influence the device performance. In this work, we explored the energetics of two oxide multilayer systems which are relevant for SOFCs components using high temperature solution calorimetry and differential scanning calorimetry (DSC). The fundamental understanding of the interfacial and structural properties of multilayers combined with the information about phase stabilities is essential in materials selection for components for intermediate temperature SOFC's. For cathode materials, we investigated the family of perovskite oxides, La0.7Sr0.3MO3, where M=Mn and Fe, as well as their solid solution phase. Manganites have been the most investigated cathode material, while the ferrites are also being considered for future use due to their thermodynamic stability and close thermal expansion coefficient with the commonly used electrolyte materials. For the bulk La0.7Sr0.3FexMn1-xO 3 solid solution, high temperature oxide melt drop solution calorimetry was performed to determine the enthalpies of formation from binary oxides and the enthalpy of mixing. It was shown that the symmetry of the perovskite structure, the valence of transition metal, and the energetics are highly interdependent and the balance between the different valence states of the Mn and Fe ions is the main factor in determining the energetics. The energetics of interfaces in multilayered structures was investigated by high temperature oxide melt solution calorimetry for the first time. The drop solution calorimetry results of La0.7Sr0.3MnO3(LSMO)/La0.7 Sr0.3FeO3(LSFO) multilayers and LSMO film are highly exothermic and differ from the bulk material with the same composition. The magnetic and electronic properties of LSMO/LSFO superlattices are highly dependent on the thickness and the structure of the individual layers. Resonant X-Ray reflectivity (XRR) technique was utilized to characterize the structure of the LSMO/LSFO superlattices. It was shown that the XRR spectra taken at the Mn and Fe absorption edges can provide more structural information than the spectra at the X-ray energy of a conventional Cu source. With this non-destructive technique, we demonstrated the ability to compare the intermixing behavior and thickness regularity throughout the thickness of different superlattice structures. For electrolyte materials, we studied the yttria stabilized zirconia (YSZ) /Al2O3 multilayer system. Differential scanning calorimetry (DSC) was used to study the crystallization of the YSZ layers to explore the effect of the interfaces on phase stabilities. It was observed that the crystallization temperature increased and the enthalpy became more exothermic as the interfacial area increased. This work demonstrated that DSC is a promising technique to study the thin film reactions and explore the interfacial enthalpies in oxide multilayer systems.

Improved thermal stability of Mn-Ir-based magnetic tunnel junction with nano-oxide layer

NASA Astrophysics Data System (ADS)

Yoon, S. Y.; Kim, Y. I.; Lee, D. H.; Kim, Y. S.; Suh, S. J.

2004-06-01

Si/SiO2/Ta/NiFe/Mn-Ir/CoFe/NOL/CoFe/Al-O/CoFe/NiFe/Ta bottom conventional (without nano-oxide layer, NOL) and specular (with NOL) MTJs were prepared by DC magnetron sputtering methods. In the case of a conventional MTJ, the TMR ratio increased up to 300 °C but the TMR ratio of a specular MTJ increased up to 400 °C. The highest TMR ratios of two samples after annealing at each optimal temperature were 21.6% (conventional MTJ) and 22.7% (specular MTJ), respectively, This improved thermal property of the specular MTJ is due to the NOL, which could act as a diffusion barrier for Mn. The bias-voltage dependence of both samples was vastly improved after annealing at each optimal temperature.

Understanding the evolution of S- and I-type granitic plutons through analysis of apatite.

NASA Astrophysics Data System (ADS)

Hess, B. L.; Fiege, A.; Tailby, N.

2017-12-01

The major and trace element composition of apatites from the Lachlan fold belt (LFB) S- and I-type granitoids (Australia) and the Central French Massif (CFM) S-type leucogranites (France) were analyzed to investigate their compositional and redox variation. Apatite is a common accessory mineral in magmatic systems that can incorporate a variety of trace elements, including the polyvalent elements sulfur (S), iron (Fe), and manganese (Mn). It was recently discovered that apatite can incorporate three oxidation states of S (S6+, S4+, S2-) into its structure as a function of oxygen fugacity [1]. However, the oxidation states of Mn and Fe in apatite are essentially unknown (2+ and/or 3+). In this study, we collected many electron probe line transects across apatites in several different host phases from a variety of S- and I-type plutons. The F-H-Cl contents of the S- and I-type LFB samples were similar ( 2.9 wt% F, 0.4 wt% Cl, 0.5 wt% OH). The CFM S-types contained virtually no Cl and ranged from near-endmember OH-apatite to near-endmember F-apatite. The apatites of all studied the S- and I-type plutons are characterized by similar ranges of Fe content (<1.5 wt% Fe), while Mn reaches much higher concentrations in the S-type when compared to I-type apatites (<6.5 wt% Mn). The S content of the apatites varies significantly, from <50 ppm S in the LFB S-types, up to 2,000 ppm S in the LFB I-types, and reaching 1,650 ppm S in the CFM S-types. The elevated S contents in the LFB I-type and CFM S-type apatites allowed us to measure the S oxidation states by using X-ray absorption near-edge structure (XANES) spectroscopy. The spectra show variability in S oxidation states ranging from mostly sulfate down to nearly equal S6+/S2- ratios, indicating redox variations during apatite formation. The S-type Mn + Fe content plots in a 1:1 ratio against calcium (Ca) in atoms per formula unit, while the I-type apatites have too low Mn and Fe to show a clear trend. Thus, divalent Mn and Fe probably replace Ca2+ in the S-types' apatite structure, while the incorporation of trivalent Mn or Fe in apatite is rather unlikely. We suggest that Mn and Fe contents in apatite may become a useful tracer of melt evolution once the distributions coefficients are experimentally calibrated. [1] Konecke et al. (2017), Am Mineral

Perovskite solid solutions with multiferroic morphotropic phase boundaries and property enhancement

NASA Astrophysics Data System (ADS)

Algueró, M.; Amorín, H.; Fernández-Posada, C. M.; Peña, O.; Ramos, P.; Vila, E.; Castro, A.

2016-05-01

Recently, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of phases in the BiFeO3-BiCoO3 perovskite binary system, associated with the existence of a discontinuous morphotropic phase boundary (MPB) between multiferroic polymorphs of rhombohedral and tetragonal symmetries. This might be a general property of multiferroic phase instabilities, and a novel promising approach for room temperature magnetoelectricity. We review here our current investigations on the identification and study of additional material systems, alternative to BiFeO3-BiCoO3 that has only been obtained by high pressure synthesis. Three systems, whose phase diagrams were, in principle, liable to show multiferroic MPBs have been addressed: the BiMnO3-PbTiO3 and BiFeO3-PbTiO3 binary systems, and the BiFeO3-BiMnO3-PbTiO3 ternary one. A comprehensive study of multiferroism across different solid solutions was carried out based on electrical and magnetic characterizations, complemented with mechanical and electromechanical measurements. An in-depth structural analysis was also accomplished when necessary.

Manganese minerals and associated fine particulates in the streambed of Pinal Creek, Arizona, U.S.A.: a mining-related acid drainage problem

USGS Publications Warehouse

Lind, Carol J.; Hem, J.D.

1993-01-01

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O2 is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed. Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek. In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn3O4 to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO3 and a 7-A?? phyllomanganate mixture of rancieite ((Ca,Mn)Mn4O9 ?? (3H2O)) and takanelite ((Mn,Ca)Mn4O9 ?? (3H2O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO3 from an anoxic groundwater that contained CO2 HCO3, and precipitated Mn3O4 and subsequently MnOOH from an oxic surface water from which most of the dissolved CO2 had been removed. It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-A?? physllomanganates. The non-magnetic <63-??m size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO3, 5% Fe (calculated as FeOOH), 2-4% exchangeable cations, and trace amounts of several silicates. ?? 1992.

Differential coordination demands in Fe vs Mn water-soluble cationic metalloporphyrins translates into remarkably different aqueous redox chemistry and biology

PubMed Central

Tovmasyan, Artak; Weitner, Tin; Sheng, Huaxin; Lu, MiaoMiao; Rajic, Zrinka; Warner, David S.; Spasojevic, Ivan; Reboucas, Julio S.; Benov, Ludmil; Batinic-Haberle, Ines

2013-01-01

The different biological behavior of cationic Fe and Mn pyridylporphyrins in Escherichia coli and mouse studies prompted us to revisit and compare their chemistry. For that purpose the series of ortho and meta isomers of Fe(III) meso-tetrakis-N-alkylpyridylporphyrins, alkyl being methyl to n-octyl, were synthesized and characterized by elemental analysis, UV/vis spectroscopy, mass spectrometry, lipophilicity, protonation equilibria of axial waters, metal-centered reduction potential, E1/2 for MIIIP/MIIP redox couple (M = Fe, Mn, P=porphyrin), kcat for the catalysis of O2•− dismutation, stability towards peroxide-driven porphyrin oxidative degradation (produced in the catalysis of ascorbate oxidation by MP), ability to affect growth of SOD-deficient E. coli and toxicity to mice. Electron-deficiency of the metal site is modulated by the porphyrin ligand, which renders Fe(III) porphyrins ≥ 5 orders of magnitude more acidic than the analogous Mn(III) porphyrins, as revealed by the pKa1 of axially coordinated waters. The 5 log units difference in the acidity between the Mn and Fe sites in porphyrin translates into the predominance of tetracationic (OH)(H2O)FeP complexes relative to pentacationic (H2O)2MnP species at pH ~7.8. This is evidenced in large differences in the thermodynamic parameters - pKa of axial waters and E1/2 of MIII/MII redox couple. The presence of hydroxo ligand labilizes trans-axial water which results in higher reactivity of Fe- relative to Mn center. The differences in the catalysis of O2•− dismutation (log kcat) between Fe and Mn porphyrins is modest, 2.5-5-fold, due to predominantly outer-sphere, with partial inner-sphere character of two reaction steps. However, the rate constant for the inner-sphere H2O2-based porphyrin oxidative degradation is 18-fold larger for (OH)(H2O)FeP than for (H2O)2MnP. The in vivo consequences of the differences between the Fe- and Mn porphyrins were best demonstrated in SOD-deficient E. coli growth. Based on fairly similar log kcat(O2.− values, very similar effect on the growth of SOD-deficient E. coli was anticipated by both metalloporphyrins. Yet, while MnTE-2-PyP5+ was fully efficacious at ≥20 μM, the Fe analog, FeTE-2-PyP5+ supported SOD-deficient E. coli growth at 200-fold lower doses in the range of 0.1 to 1 μM. Moreover the pattern of SOD-deficient E. coli growth was different with Mn- and Fe porphyrins. Such results suggested different mode of action of these metalloporphyrins. Further exploration demonstrated that: (1) 0.1 μM FeTE-2-PyP5+ provided similar growth stimulation as 0.1 μM Fe salt, while 20 μM Mn salt provides no protection to E. coli; and (2) 1 μM Fe porphyrin is fully degraded by 12 hours in E. coli cytosol and growth medium; while Mn porphyrin is not. Stimulation of the aerobic growth of SOD-deficient E. coli by the Fe porphyrin is therefore due to iron acquisition. Our data suggest that in vivo, redox-driven degradation of Fe porphyrins resulting in Fe release plays a major role in their biological action. Possibly, iron reconstitutes enzymes bearing [4Fe-4S] clusters as active sites. Under same experimental conditions, (OH)(H2O)FePs do not cause mouse arterial hypotension, whereas (H2O)2MnPs do, which greatly limits the application of Mn porphyrins in vivo. PMID:23646875

A Structural Molar Volume Model for Oxide Melts Part I: Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 Melts—Binary Systems

NASA Astrophysics Data System (ADS)

Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

2016-04-01

A structural molar volume model was developed to accurately reproduce the molar volume of molten oxides. As the non-linearity of molar volume is related to the change in structure of molten oxides, the silicate tetrahedral Q-species, calculated from the modified quasichemical model with an optimized thermodynamic database, were used as basic structural units in the present model. Experimental molar volume data for unary and binary melts in the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-Al2O3-SiO2 system were critically evaluated. The molar volumes of unary oxide components and binary Q-species, which are model parameters of the present structural model, were determined to accurately reproduce the experimental data across the entire binary composition in a wide range of temperatures. The non-linear behavior of molar volume and thermal expansivity of binary melt depending on SiO2 content are well reproduced by the present model.

Novel processes for anaerobic sulfate production from elemental sulfur by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1994-01-01

Sulfate reducers and related organisms which had previously been found to reduce Fe(III) with H2 or organic electron donors oxidized S0 to sulfate when Mn(IV) was provided as an electron acceptor. Organisms catalyzing this reaction in washed cell suspensions included Desulfovibrio desulfuricans, Desulfomicrobium baculatum. Desulfobacterium autotrophicum, Desulfuromonas acetoxidans, and Geobacter metallireducens. These organisms produced little or no sulfate from S0 with Fe(III) as a potential electron acceptor or in the absence of an electron acceptor. In detailed studies with Desulfovibrio desulfuricans, the stoichiometry of sulfate and Mn(II) production was consistent with the reaction S0 + 3 MnO2 + 4H+ ???SO42- + 3Mn(II) + 2H2O. None of the organisms evaluated could be grown with S0 as the sole electron donor and Mn(IV) as the electron acceptor. In contrast to the other sulfate reducers evaluated, Desulfobulbus propionicus produced sulfate from S0 in the absence of an electron acceptor and Fe(III) oxide stimulated sulfate production. Sulfide also accumulated in the absence of Mn(IV) or Fe(III). The stoichiometry of sulfate and sulfide production indicated that Desulfobulbus propionicus disproportionates S0 as follows: 4S0 + 4H2O???SO42- + 3HS- + 5 H+. Growth of Desulfobulbus propionicus with S0 as the electron donor and Fe(III) as a sulfide sink and/or electron acceptor was very slow. The S0 oxidation coupled to Mn(IV) reduction described here provides a potential explanation for the Mn(IV)-dependent sulfate production that previous studies have observed in anoxic marine sediments. Desulfobulbus propionicus is the first example of a pure culture known to disproportionate S0.

The Effects of Bismuth Oxide on Microstructures and Magnetic Properties of Mn-Mg-Al Ferrites

NASA Astrophysics Data System (ADS)

Nekouee, Kh. A.; Rahimi, A. H.; Haghighi, M. Alineghad; Ehsani, N.

2018-04-01

In the present paper, the effects of bismuth oxide as an additive on microstructure and magnetic properties of Mg0.9Mn0.1Al0.4Fe1.6O4 were investigated. Mg-Mn-Al ferrite powders were prepared by the conventional solid state synthesis method. Two different amounts of bismuth oxide (2.5 wt.% and 5 wt.%) were utilized as the sintering aid and their microstructure and physical properties were compared to those of the sample without additives. X-ray diffraction (XRD) analysis indicated that crystal lattice distortion due to the microstructural constraints as the result from incorporation of bismuth oxide into the microstructure was developed by adding bismuth oxide. XRD Rietveld refinement was used to define the cation distribution and to refine the lattice parameter and oxygen parameter for the sample without bismuth oxide as (Mg0.16Mn0.02Al0.15Fe0.77)A(Mg0.74Mn0.08Al0.25Fe0.83)BO4 and 8.3308 Å and 0.2542, respectively. Microstructure studies show that a bismuth rich liquid phase forms during the sintering at 1250°C, which enhances the densification of sintered bodies up to 13% (a relative density of 93%). Magnetization of sintered samples were increased from 21.1 emu/g to 26.2 emu/g upon addition of 2.5 wt.% bismuth oxide and then decreased to 24.9 emu/g when 5 wt.% bismuth oxide was added.

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manganese in Endeavour Crater Rim Materials, Mars, and Implications for Habitability

NASA Astrophysics Data System (ADS)

Arvidson, R. E.; Catalano, J. G.; Clark, B. C.; Fischer, W. W.; Grotzinger, J. P.; Gellert, R.; Guinness, E. A.; Herkenhoff, K. E.; Johnson, J. R.; McLennan, S. M.; Ming, D. W.; Morris, R. V.; Squyres, S. W.; Yen, A. S.

2014-12-01

The Opportunity Mars rover wheels overturned two adjacent rocks and exposed underlying fracture-filling deposits while exploring the Murray Ridge rim segment of the Noachian-aged Endeavour Crater. These two small rocks, Pinnacle Island (~4 cm across) and Stuart Island (ranging from ~3 to 8 cm wide and ~10 cm long), were subsequently examined in detail to determine the textures, spectral reflectances (0.4 to 1.0 μm), and compositions of the fracture-filling materials. Relatively bright materials with a composition enriched in Mg, Fe, and S, and spectral features indicative of hydrated sulfates, are overlain with a dark, purple mineral phase or phases with a composition enriched in Mn, Ni, P, and Ca, all relative to underlying bedrock. Reflectance spectra for the dark, purple material are consistent with the presence of one or more Mn-oxide phases. Results indicate two aqueous events, one to deposit the Fe and Mg-rich sulfates, and one to deposit the Mn-rich mineral(s), perhaps with scavenging of Ni from the fluid. Ca and P-rich phases (e.g., Ca-phosphates) co-precipitated with Mn-bearing mineral(s) or were incorporated into one or more of them. Mixing of reducing ground waters with an oxidizing atmosphere or other waters likely produced both the S and Mn-enriched deposits. Oxidation of Mn, in particular, requires a very high potential oxidant relative to what is required for S or Fe oxidation. This suggests oxidation by O2 or species derived from O2. Mn-oxide phases would have provided highly favorable substrates for microbial respiration, making this period of aqueous flow through the fractures a potentially habitable environment. These results add to the evolving story of aqueous alteration of Endeavour's rim rocks, including evidence for nontronite, montmorillonite, Ca-sulfate-rich veins, and hematitic concretions.

Half-metallic Co-based quaternary Heusler alloys for spintronics: Defect- and pressure-induced transitions and properties

DOE PAGES

Enamullah, .; Johnson, D. D.; Suresh, K. G.; ...

2016-11-07

Heusler compounds offer potential as spintronic devices due to their spin polarization and half-metallicity properties, where electron spin-majority (minority) manifold exhibits states (band gap) at the electronic chemical potential, yielding full spin polarization in a single manifold. Yet, Heuslers often exhibit intrinsic disorder that degrades its half-metallicity and spin polarization. Using density-functional theory, we analyze the electronic and magnetic properties of equiatomic Heusler (L2 1) CoMnCrAl and CoFeCrGe alloys for effects of hydrostatic pressure and intrinsic disorder (thermal antisites, binary swaps, and vacancies). Under pressure, CoMnCrAl undergoes a metallic transition, while half-metallicity in CoFeCrGe is retained for a limited range.more » Antisite disorder between Cr-Al pair in CoMnCrAl alloy is energetically the most favorable, and retains half-metallic character in Cr-excess regime. However, Co-deficient samples in both alloys undergo a transition from half-metallic to metallic, with a discontinuity in the saturation magnetization. For binary swaps, configurations that compete with the ground state are identified and show no loss of half-metallicity; however, the minority-spin band gap and magnetic moments vary depending on the atoms swapped. For single binary swaps, there is a significant energy cost in CoMnCrAl but with no loss of half-metallicity. Although a few configurations in CoFeCrGe energetically compete with the ground state, the minority-spin band gap and magnetic moments vary depending on the atoms swapped. Furthermore, this information should help in controlling these potential spintronic materials.« less

Half-metallic Co-based quaternary Heusler alloys for spintronics: Defect- and pressure-induced transitions and properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Enamullah, .; Johnson, D. D.; Suresh, K. G.

Heusler compounds offer potential as spintronic devices due to their spin polarization and half-metallicity properties, where electron spin-majority (minority) manifold exhibits states (band gap) at the electronic chemical potential, yielding full spin polarization in a single manifold. Yet, Heuslers often exhibit intrinsic disorder that degrades its half-metallicity and spin polarization. Using density-functional theory, we analyze the electronic and magnetic properties of equiatomic Heusler (L2 1) CoMnCrAl and CoFeCrGe alloys for effects of hydrostatic pressure and intrinsic disorder (thermal antisites, binary swaps, and vacancies). Under pressure, CoMnCrAl undergoes a metallic transition, while half-metallicity in CoFeCrGe is retained for a limited range.more » Antisite disorder between Cr-Al pair in CoMnCrAl alloy is energetically the most favorable, and retains half-metallic character in Cr-excess regime. However, Co-deficient samples in both alloys undergo a transition from half-metallic to metallic, with a discontinuity in the saturation magnetization. For binary swaps, configurations that compete with the ground state are identified and show no loss of half-metallicity; however, the minority-spin band gap and magnetic moments vary depending on the atoms swapped. For single binary swaps, there is a significant energy cost in CoMnCrAl but with no loss of half-metallicity. Although a few configurations in CoFeCrGe energetically compete with the ground state, the minority-spin band gap and magnetic moments vary depending on the atoms swapped. Furthermore, this information should help in controlling these potential spintronic materials.« less

Arsenic release from Fe/Mn oxide-rich (model) soils/sediments - A comparison of single extraction procedures

NASA Astrophysics Data System (ADS)

Vanek, A.; Komarek, M.; Galuskova, I.

2012-04-01

Arsenic extractability in As-modified Fe(III) and Mn(III,IV) oxide-coated sands was tested using five widely used 2-h single extraction procedures: deionised water, 0.01 M CaCl2, 1 M NH4NO3, 0.1 M Na2HPO4 and 0.005 DTPA. In general, the highest As recoveries reaching 39-50% of total As concentration were observed for all extracting media in the birnessite (delta-MnO2) system, indicating relatively weak adsorption of As onto the Mn oxides. The Na2HPO4 extracts from the Fe oxide systems (i.e., associated with ferrihydrite and goethite) were highest in As, accounting for up to 34% of total As amount. Surprisingly, comparable recoveries of As (14-20%) yielded deionised water, CaCl2, NH4NO3, DTPA as extracting media for both ferrihydrite and goethite coatings. Deionised water and Na2HPO4 extractions are suggested for quick estimation of easily soluble, exchangeable and/or specifically adsorbed As in real soil/sediment samples.

Mercury- and silver-rich ferromanganese oxides, southern California Borderland: Deposit model and environmental implications

USGS Publications Warehouse

Hein, J.R.; Koschinsky, A.; McIntyre, B.R.

2005-01-01

Mercury- and silver-enriched ferromanganese oxide crusts were recovered at water depths of 1,750 tol,300 m from La Victoria knoll, located about 72 km off the coast of northern Baja California. No other ferromanganese precipitate found so far in the modern ocean basins is similarly enriched in Hg and Ag. The precipitates consist of submetallic gray, brecciated, Mn oxide layers overlain by brown earthy, laminated Fe-Mn oxide crusts. Both oxide types are rich in Hg (to 10 ppm) and Ag (to 5.5 ppm). The Mn-rich layers are composed of ??MnO2, with lesser amounts of 10A?? and 7A?? manganates, whereas the Mn phase in the Fe-Mn crusts is solely ??MnO2. The Fe phase in both layers is X-ray amorphous. Established criteria for distinguishing hydrothermal versus hydrogenetic crusts indicate that the Mn-rich layers are predominantly of low-temperature hydrothermal origin, whereas the Fe-Mn crusts are hydrogenetic, although there is some overlap in the source of chemical components in both types. La Victoria knoll is uplifted continental basement rock with basalt, andesite, and schist cropping out at the surface; the knoll may have an intrusive core. The Hg and Ag were derived from leaching by hydrothermal fluids of organic matter-rich sediments in basins adjacent to La Victoria knoll and, to a lesser extent, from continental basement rocks underlying the knoll and adjacent basins. Both rock types are notably enriched in Ag and Hg. Faults were the main fluid transport pathway, and hydrothermal circulation was driven by high heat flow associated with thinned crust. Other elements derived from the hydrothermal fluids include Tl, Cd, Cr, and Li. The main host for Hg and Ag is FeOOH, although MnO2 likely hosts some of the Ag. Minor sulfide and barite also may contain small amounts of these metals. Possible analogs in the geologic record for this deposit type are found in the Basin and Range province of the western United States and Mexico. The discovery highlights the fact that fluids circulating along faults in the offshore California borderland are transporting potentially toxic metals (Hg, Ag, Tl, As, Cd, Cr, Pb, and Ni) and depositing them on and just below the ocean floor. ?? 2005 Society of Economic Geologists, Inc.

Kinetics and mechanism of diclofenac removal using ferrate(VI): roles of Fe3+, Fe2+, and Mn2.

PubMed

Zhao, Junfeng; Wang, Qun; Fu, Yongsheng; Peng, Bo; Zhou, Gaofeng

2018-06-01

In this study, the effect of Fe 3+ , Fe 2+ , and Mn 2+ dose, solution pH, reaction temperature, background water matrix (i.e., inorganic anions, cations, and natural organic matters (NOM)), and the kinetics and mechanism for the reaction system of Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ were investigated systematically. Traces of Fe 3+ , Fe 2+ , and Mn 2+ promoted the DCF removal by Fe(VI) significantly. The pseudo-first-order rate constant (k obs ) of DCF increased with decreasing pH (9-6) and increasing temperature (10-30 °C) due to the gradually reduced stability and enhanced reactivity of Fe(VI). Cu 2+ and Zn 2+ ions evidently improved the DCF removal, while CO 3 2- restrained it. Besides, SO 4 2- , Cl - , NO 3 - , Mg 2+ , and Ca 2+ almost had no influence on the degradation of DCF by Fe(VI)/Fe 3+ , Fe(VI)/Fe 2+ , and Fe(VI)/Mn 2+ within the tested concentration. The addition of 5 or 20 mg L -1 NOM decreased the removal efficiency of DCF. Moreover, Fe 2 O 3 and Fe(OH) 3 , the by-products of Fe(VI), slightly inhibited the DCF removal, while α-FeOOH, another by-product of Fe(VI), showed no influence at pH 7. In addition, MnO 2 and MnO 4 - , the by-products of Mn 2+ , enhanced the DCF degradation due to catalysis and superposition of oxidation capacity, respectively. This study indicates that Fe 3+ and Fe 2+ promoted the DCF removal mainly via the self-catalysis for Fe(VI), and meanwhile, the catalysis of Mn 2+ and the effect of its by-products (i.e., MnO 2 and MnO 4 - ) contributed synchronously for DCF degradation. Graphical abstract ᅟ.

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope budget. In contrast, the isotopic composition of W in ancient seawater should have evolved in response to the extent of deposition of both Fe and Mn oxides; this is likely to be different compared with that of the Mo isotopes, which is strongly associated with the occurrence of Mn oxides relative to Fe oxides.

Large-scale phase separation with nano-twin domains in manganite spinel (Co,Fe,Mn){sub 3}O{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horibe, Y., E-mail: horibe@post.matsc.kyutech.ac.jp; Takeyama, S.; Mori, S.

The effect of Mn concentration on the formation of nano-domain structures in the spinel oxide (Co,Fe,Mn){sub 3}O{sub 4} was investigated by electron diffraction, bright-, and dark-field imaging technique with transmission electron microscopy. Large scale phase separation with nano-twin domains was observed in Co{sub 0.6}Fe{sub 1.0}Mn{sub 1.4}O{sub 4}, in contrast to the highly aligned checkerboard nano-domains in Co{sub 0.6}Fe{sub 0.9}Mn{sub 1.5}O{sub 4}. Diffusion of the Mn{sup 3+} ions with the Jahn-Teller distortions is suggested to play an important role in the formation of checkerboard nano-domain structure.

Composition and genesis of ferromanganese deposits from the northern South China Sea

NASA Astrophysics Data System (ADS)

Zhong, Yi; Chen, Zhong; González, Francisco Javier; Hein, James R.; Zheng, Xufeng; Li, Gang; Luo, Yun; Mo, Aibin; Tian, Yuhang; Wang, Shuhong

2017-05-01

Marine ferromanganese (Fe-Mn) nodules and crusts are archives of past environmental conditions and potential mineral resources. Over the last 30 years, many have been discovered in the northern South China Sea (SCS). To determine the origin of the Fe-Mn deposits, a comprehensive laboratory analysis of physical properties, mineralogy and geochemistry was conducted on newly collected Fe-Mn nodule/crust samples. The results revealed that there are three types of Fe-Mn deposits: (1) Fe-rich nodules containing essentially goethite occur on the northeastern slope of the SCS, with high Fe, low Mn (Mn/Fe = 0.03) and low trace metals and rare earth elements concentrations; (2) Smooth Fe-Mn nodules and crusts composed of asbolane, todorokite and CFA occur along the northwestern marginal of the SCS that have similar Fe and Mn contents (Mn/Fe = 1.21), moderate trace metal enrichments, and a positive Ce anomaly; (3) Fe-Mn nodules and crusts composed of asbolane, todorokite and birnessite that occur in the central basin of the SCS have higher Mn and lower Fe contents (Mn/Fe = 1.45). This depositional pattern was associated with major changes in oceanographic conditions and tectonic regimes. The northeastern slope deposits occur in a contourite depositional system, are strongly enriched in Fe relative to Mn (average 38.7% and 0.96%, respectively), formed from the combination of hydrogenetic and diagenetic processes. We propose a new genetic model for Fe-Mn nodules, which formed through the oxidation of pyrite and pyrite-barite concretions that formed by rapid early diagenetic growth (average 3320 mm/Myr) on continental margins above the carbonate compensation depth, and dominated by hydrocarbon seep structures and strong erosive action of bottom currents along the northeastern slope. In contrast, the introduction of vigorous deep-water flow from the North Pacific promoted the slow growth (4-7 mm/Myr) of hydrogenetic Fe-Mn nodules and crusts along the northwestern margin. Finally, hydrogenetic growth of Fe-Mn nodules and crusts in the central basin may have been enhanced by volcanic processes. Our data provide new insights into the genesis and province characteristics of the Fe-Mn nodules and crusts of the northern SCS.

Spatio-temporal Distribution and Chemical Speciation of Iron and Manganese in Sediments from Lake Aha, China

NASA Astrophysics Data System (ADS)

Liu, Feng; Hu, Jiwei; Qin, Fanxin; Jiang, Cuihong; Huang, Xianfei; Deng, Jiajun; Li, Cunxiong

2010-11-01

This paper reports an investigation on pollution and potential risk on elements of iron (Fe) and manganese (Mn) in sediments from Lake Aha, which is a drinking-water source for Guiyang City, the capital of Guizhou Province in southwestern China. In the present research, chemical speciation of Fe and Mn in sediments from the lake was studied based on the sequential extraction procedure developed by Tessier et al.. The results obtained from the study are as follows. The average values of total Fe were 47617 mg/kg and 70325 mg/kg in sediments from the lake in summer and winter respectively, and its speciation consisted mainly of residual and Fe-Mn oxides fractions. The amounts of total Fe and the distribution of its speciation in the sediments should be affected by effluents from a large quantity of deserted coal mines in the lake basin in summer and winter. The average values of total Mn were 7996 mg/kg and 1753 mg/kg in summer and winter respectively, and its speciation is primarily comprised of carbonate and Fe-Mn oxides fractions. The amounts of total Mn and its distribution in different fractions in the sediments were believed to be primarily influenced by effluents from those deserted coal mines in summer and by the condition of redox interface in winter.

Anaerobic biodegradation of BTEX using Mn(IV) and Fe(III) as alternative electron acceptors.

PubMed

Villatoro-Monzón, W R; Mesta-Howard, A M; Razo-Flores, E

2003-01-01

Anaerobic BTEX biodegradation was tested in batch experiments using an anaerobic sediment as inoculum under Fe(III) and Mn(IV) reducing conditions. All BTEX were degraded under the conditions tested, specially under Mn(IV) reducing conditions, where benzene was degraded at a rate of 0.8 micromol l(-1) d(-1), significantly much faster than Fe(III) reducing conditions. Under Fe(III) reducing conditions, ethylbenzene was the compound that degraded at the faster rate of 0.19 micromol l(-1) d(-1). Mn(IV) reducing conditions are energetically more favourable than Fe(III), therefore, BTEX were more rapidly degraded under Mn(IV) reducing conditions. These results represent the first report of the degradation of benzene with Mn(IV) as the final electron acceptor. Amorphous manganese oxide is a natural widely distributed metal in groundwater, where it can be microbiologically reduced, leading to the degradation of monoaromatic compounds.

Ferromanganese crusts and nodules, rocks that grow

USGS Publications Warehouse

Mizell, Kira; Hein, James

2016-01-01

Ferromanganese (Fe-Mn) crusts and nodules are marine sed- imentary mineral deposits, composed mostly of iron and manganese oxides. They precipitate very slowly from seawa- ter, or for nodules also from deep-sea sediment pore waters, recording the chemical signature of these source waters as they grow. Additional elements incorporate via sorption pro- cesses onto the Fe-Mn oxides, including rare and valuable metals that can reach concentrations that are economically valuable.

Magnetotransport and interdiffusion characteristics of magnetic tunnel junctions comprising nano-oxide layers upon exposure to postdeposition annealing

NASA Astrophysics Data System (ADS)

Chu, In Chang; Song, Min Sung; Chun, Byong Sun; Lee, Seong Rae; Kim, Young Keun

2005-08-01

Magnetic tunnel junction (MTJ) structures based on underlayer (CoNbZr)/bufferlayer (CoFe)/antiferromagnet (IrMn)/pinned layer (CoFe)/tunnel barrier (AlO x)/free layer (CoFe)/capping (CoNbZr) have been prepared to investigate thermal degradation of magnetoresistive responses. Some junctions possess a nano-oxide layer (NOL) inside either in the underlayer or bufferlayer. The main purpose of the NOL inclusion was to control interdiffusion path of Mn from the antiferromagnet so that improved thermal stability could be achieved. The MTJs with NOLs were found to have reduced interfacial roughness, resulting in improved tunneling magnetoresistance (TMR) and reduced interlayer coupling field. We also confirmed that the NOL effectively suppressed the Mn interdiffusion toward the tunnel barrier by dragging Mn atoms toward NOL during annealing.

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

USGS Publications Warehouse

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.

Degradation of sulfamethazine using Fe3O4-Mn3O4/reduced graphene oxide hybrid as Fenton-like catalyst.

PubMed

Wan, Zhong; Wang, Jianlong

2017-02-15

In this paper, Fe 3 O 4 -Mn 3 O 4 /reduced graphene oxide (RGO) hybrid was synthesized through polyol process and impregnation method and used as heterogeneous Fenton-like catalyst for degradation of sulfamethazine (SMT) in aqueous solution. The hybrid catalyst had higher catalytic efficiency compared with Fe 3 O 4 -Mn 3 O 4 and Mn 3 O 4 as catalyst for degradation of SMT . The effects of pH value, H 2 O 2 concentration, catalyst dosage, initial SMT concentration and temperature on SMT degradation were investigated. The removal efficiency of SMT was about 98% at following optimal conditions: pH=3, T=35°C, Fe 3 O 4 /Mn 3 O 4 -RGO composites=0.5g/L, H 2 O 2 =6mM. The inhibitor experiments indicated that the main active species was hydroxyl radicals (·OH) on catalyst surface. At last, the possible catalytic mechanism was proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

Evaluation of distribution and manganese availability in soils under soybean cultivation

NASA Astrophysics Data System (ADS)

Mendes Coutinho, Edson Luiz; de Cássia Gomes São João, Andréia; Mendes Coutinho Neto, André; Corá, José Eduardo; Fernandes, Carolina

2013-04-01

Manganese (Mn) deficiency in soybean became a problem in Brazil, mainly, due to soil low fertility use or soil high pH due to incorrect lime use. However, the manganese deficiency have not been thoroughly investigated. The effect of Mn soil application on Mn distribution among exchangeable, organic matter, amorphous Fe and Al oxides, crystalline Fe and Al oxides, and residual fractions were studied on a Typic Quartzipsament (RQ), a clayey Typic Haplustox (LVA) and a sandy clay loam Typic Haplustox (LV), in a greenhouse experiment carried out in Jaboticabal (SP) - Brazil (21°14'05'' S and 48°17'09'' W). A complete randomized design with three replications of treatments in a 3 x 6 factorial arrangement (three soils and six manganese rates) was used. Five soybean plants were grown during 34 days in pots with 2.5 kg of soil. The Mn contents in these fractions were correlated with those extracted by DTPA and by Mehlich-1 extractants and with soybean shoot Mn contents. Mn rates (0, 5, 10, 20, 40 and 60 mg kg-1) were applied using manganese sulphate (MnSO4). In the Oxisols, most of the Mn was associated with the Fe and Al oxides (amorphous and crystalline) and residual fractions. In the sandy soil (RQ), higher contents were found in exchangeable and residual fractions. Exchangeable fraction was the most important Mn supplier to soybean plants. Multiple regression analysis showed that Mn extracted by DTPA and Mehlich-1 were associated with soil exchangeable fraction.

Oxidation Of Manganese At Kimberley, Gale Crater: More Free Oxygen In Mars' Past?

NASA Technical Reports Server (NTRS)

Lanza, N. L.; Wiens, R. C.; Arvidson, R. E.; Clark, B. C.; Fischer, W. W.; Gellert, R.; Grotzinger, J. P.; Hurowitz, J. A.; McLennan, S. M.; Morris, R. V.;

Extraction of manganese from electrolytic manganese residue by bioleaching.

PubMed

Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

2011-01-01

Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. Copyright © 2010 Elsevier Ltd. All rights reserved.

Isolation and Characterization of Microbes Mediating Thermodynamically Favorable Coupling of Anaerobic Oxidation of Methane and Metal Reduction

NASA Astrophysics Data System (ADS)

Glass, J. B.; Reed, B. C.; Sarode, N. D.; Kretz, C. B.; Bray, M. S.; DiChristina, T. J.; Stewart, F. J.; Fowle, D. A.; Crowe, S.

2014-12-01

Methane is the third most reduced environmentally relevant electron donor for microbial metabolisms after organic carbon and hydrogen. In anoxic ecosystems, the major sink for methane is anaerobic oxidation of methane (AOM) mediated by syntrophic microbial consortia that couple AOM to reduction of an oxidized electron acceptor to yield free energy. In marine sediments, AOM is generally coupled to reduction of sulfate despite an extremely small amount of free energy yield because sulfate is the most abundant electron acceptor in seawater. While AOM coupled to Fe(III) and Mn(IV) reduction (Fe- and Mn-AOM) is 10-30x more thermodynamically favorable than sulfate-AOM, and geochemical data suggests that it occurs in diverse environments, the microorganisms mediating Fe- and Mn-AOM remain unknown. Lake Matano, Indonesia is an ideal ecosystem to enrich for Fe- and Mn-AOM microbes because its anoxic ferruginous deep waters and sediments contain abundant Fe(III), Mn(IV) and methane, and extremely low sulfate and nitrate. Our research aims to isolate and characterize the microbes mediating Fe- and Mn-AOM from three layers of Lake Matano sediments through serial enrichment cultures in minimal media lacking nitrate and sulfate. 16S rRNA amplicon sequencing of sediment inoculum revealed the presence of the Fe(III)-reducing bacterium Geobacter (5-10% total microbial community in shallow sediment and 35-60% in deeper sediment) as well as 1-2% Euryarchaeota implicated in methane cycling, including ANME-1 and 2d and Methanosarcinales. After 90 days of primary enrichment, all three sediment layers showed high levels of Fe(III) reduction (60-90 μM Fe(II) d-1) in the presence of methane compared to no methane and heat-killed controls. Treatments with added Fe(III) as goethite contained higher abundances of Geobacter than the inoculum (60-80% in all layers), suggesting that Geobacter may be mediating Fe(III) reduction in these enrichments. Quantification of AOM rates is underway, and will be used to estimate the plausibility of metal-AOM as a thermodynamically favorable methane sink in anoxic ecosystems of both the modern and ancient Earth.

Influence of extractable soil manganese on oxidation capacity of different soils in Korea

NASA Astrophysics Data System (ADS)

Chon, Chul-Min; Kim, Jae Gon; Lee, Gyoo Ho; Kim, Tack Hyun

2008-08-01

We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00-0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mnd), NH2OH·HCl (Mnh), and hydroquinone (Mnr) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH2OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH2OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mnd, Mnh, and Mnr showed a relatively high correlation with the Cr tests ( r = 0.655-0.851; P < 0.01). The concentrations of Mnd and Mnh were better correlated with the Cr oxidation tests than was the Mnr concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mnd and Mnh than by Mnr. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).

Efficient catalytic As(III) oxidation on the surface of ferrihydrite in the presence of aqueous Mn(II).

PubMed

Lan, Shuai; Ying, Hong; Wang, Xiaoming; Liu, Fan; Tan, Wenfeng; Huang, Qiaoyun; Zhang, Jing; Feng, Xionghan

2018-01-01

Arsenic is a carcinogenic element that exists primarily as arsenate [As(V)] and arsenite [As(III)] in the nature environment, with As(III) being more toxic and mobile of the two species. In addition, ferrihydrite, which is widely distributed in soils and aquatic environments, can catalyze the oxidation of Mn(II) and accelerate the formation of high-valence Mn, which can significantly influence the speciation, toxicity, and mobility of As when these species co-exist. In this context, we herein explored the mechanism of As(III) oxidation in the presence of ferrihydrite and Mn(II) using a kinetic approach combined with multiple spectroscopic techniques, including X-ray absorption near edge spectroscopy, in situ horizontal attenuated total-reflectance Fourier transform infrared spectroscopy, and in situ quick scanning X-ray absorption spectroscopy. Our results indicate that efficient As(III) oxidation by dissolved O 2 occurs on the surface of ferrihydrite in the presence of aqueous Mn(II). Compared with As(III) oxidation in the presence of ferrihydrite and Mn oxides (i.e., Mn oxides/hydroxides), the degree of As(III) oxidation in the ferrihydrite-Mn(II) system was significantly higher, and the majority of generated As(V) was adsorbed on the mineral (i.e., ferrihydrite) surface. Furthermore, As(III) oxidation was enhanced upon increasing both the molar ratio of Mn(II)/As(III) and the solution pH. The greater As(III) oxidation by O 2 in the ferrihydrite-Mn(II) system was mainly attributed to the formation of a strong oxidant of the instantaneous intermediate Mn(III) species via Mn(II) oxidation under catalysis by the ferrihydrite surface. Moreover, As(III) oxidation occurred mainly on the ferrihydrite surface and was accompanied by the regeneration of Mn(II), thereby rendering it recyclable. These results therefore provide new insights into the mechanism of As(III) oxidation on the surfaces of Fe oxides (i.e., Fe oxides/hydroxides) in the presence of aqueous Mn(II) as well as the new details regarding the electron transfer mechanisms between the As(III)-Mn(II, III)-O 2 species at the ferrihydrite surface, and could lead to novel approaches for As(III) contaminant remediation in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ecosystems supporting clusters of sporadic TSEs demonstrate excesses of the radical-generating divalent cation manganese and deficiencies of antioxidant co factors Cu, Se, Fe, Zn. Does a foreign cation substitution at prion protein's Cu domain initiate TSE?

PubMed

Purdey, M

2000-02-01

Analyses of food chains supporting isolated clusters of sporadic TSEs (CWD in N Colorado, scrapie in Iceland, CJD in Slovakia) demonstrate a consistent 2 1/2+ fold greater concentration of the pro-oxidant divalent cation, manganese (Mn), in relation to normal levels recorded in adjoining TSE-free localities. Deficiencies of the antioxidant co factors Cu/Se/Zn/Fe and Mg, P and Na were also consistently recorded in TSE foodchains. Similarities between the clinical/pathological profile of TSEs and Mn delayed psycho-neurotoxicity in miners are cited, and a novel theory generated which suggests that sporadic TSE results from early life dependence of TSE susceptible genotypes on ecosystems characterised by this specific pattern of mineral imbalance. Low Cu/Fe induces an excessive absorption of Mn in ruminants and an increased oxidation of Mn2+ into its pro oxidant species, Mn3+, which accumulates in mitochondria of CNS astrocytes in Mn SOD deficient genotypes. Deficiencies of scavenger co factors Cu/Zn/Se/Fe in the CNS permits Mn3+ initiated chain reactions of auto-oxidant mediated neuronal degeneration to proliferate, which, in turn, up-regulates the expression of the Cu-metalloprotein, prion protein (PrP). Once the rate of PrP turnover and its demand for Cu exceeds the already depleted supply of Cu within the CNS, PrP can no longer bind sufficient Cu to maintain its conformation. Mn3+ substitutes at the vacated Cu domain on PrP, thus priming up a latent capacity for lethal auto-oxidative activity to be carried along with PrP like a 'trojan horse'; where Mn 3+ serves as the integral 'infectious' transmissible component of the misfolded PrP-cation complex. The Mn overactivation of concanavalin A binding to glycoprotein and Mn-initiated autoxidation results in a diverse pathological profile involving receptor capping, aggregation/modification of CNS membrane/cytoskeletal proteins. TSE ensues. The BSE/nv CJD strain entails a 'synthetic' induction of the same CNS mineral disturbance, where 'in utero' exposure to Cu-chelating insecticides/Mn supplements accelerates the onset of a more virulent 'strain' of adolescent TSE. Copyright 2000 Harcourt Publishers Ltd.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Expert Assessment of Advanced Power Sources

DTIC Science & Technology

2007-07-01

including [13] LiCo1-yNiyO2 , LiNiO2, LiMnO2, LiMn2O4, LiV2O5 and LiFePO4 . The last compound, lithium iron phosphate [19], is attractive as iron is...cheaper and more environmentally friendly than cobalt, nickel or manganese. Commercial development of a lithium ion battery based on LiFePO4 is...electrochemical performance evaluated. Materials studied include: LiV2O5 and other vanadium oxides, LiCoO2, LiMnO2, LiMn2O4 and LiFePO4 . 3-D

Two-Oxide Disequilibrium: A New Geospeedometer Based on Diffusion in Ilmenite

NASA Astrophysics Data System (ADS)

Williams, K. B.; Krawczynski, M. J.; Van Orman, J. A.

2016-12-01

Diffusion-annealing experiments were conducted in a 0.5" piston cylinder apparatus to investigate diffusivity of Fe2+, Mg2+, and Mn2+ in ilmenite solid solutions between 800ºC and 1000ºC. Polycrystalline ilmenite (FeTiO3) was juxtaposed against either an oriented geikielite (MgTiO3) single crystal or polycrystalline Mn-bearing (5 mol% Mn) ilmenite, in a "diffusion-couple" geometry. Geikielite single crystals were synthesized at Los Alamos National Laboratory, cut into 1 mm edge-length cubes, and polished either perpendicular or parallel to the c-axis. Polycrystalline ilmenite starting materials were synthesized by mixing high purity reagent-grade oxides (FeO, MnO, and TiO2) and sintering in a piston cylinder apparatus, then cut into wafers and polished. Experimental run products were analyzed by electron microprobe at Washington University in St. Louis. Microprobe analyses were obtained perpendicularly across the diffusion interface for each experiment. Experimental diffusion profiles create smooth curves that, when fit with an error function, define Fe-Mg and Fe-Mn interdiffusion coefficients in ilmenite. The diffusion coefficients do not appear compositionally dependent, but do show significant anisotropy. Preliminary results suggest diffusion activation energies are lower in ilmenite than in titanomagnetite [1]. Ilmenite-titanomagnetite equilibria define pre-eruptive temperatures and oxygen fugacities. However, oxides often exist out of equilibrium [2]. We use the cation diffusion data for ilmenite and existing data on titanomagnetite to establish two-oxide disequilibrium as a geospeedometer. Our data constrain oxide-oxide re-equilibration timescales at Mt. Unzen to months, consistent with estimates from zoned, single crystals of magnetite [3,4]. Future experiments will examine the effect of oxygen fugacity on diffusivity in ilmenite solid solutions. References:[1] Van Orman & Crispin (2010) RiMG 72, 757-825.[2] Bacon & Hirschmann (1988) Am. Min. 73, 57-61.[3] Nakamura (1995) Geology 23, 807-810.[4] Venezky & Rutherford (1999) J. Volc. Geo. Res. 89, 213-230.

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity.

PubMed

Semin, B К; Davletshina, L N; Seibert, M; Rubin, A B

2018-01-01

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2 Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH5.7) than at neutral pH (3Mn/RC are extracted at pH6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H 2 Q action, since H 2 Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H 2 Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O 2 at a low rate in the presence of exogenous Ca 2+ (at about 27% of the rate of O 2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O 2 by the 3Mn/1Fe cluster or apparent O 2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE PAGES

Hausladen, Debra M.; Fendorf, Scott

2017-01-13

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Hexavalent Chromium Generation within Naturally Structured Soils and Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hausladen, Debra M.; Fendorf, Scott

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases$-$Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides—that lead to its production. Here in this paper, we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH) 3- and Cr 0.25Fe 0.75(OH) 3-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregatesmore » simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.« less

Linking Mn(II)-oxidizing bacteria to natural attenuation at a former U mining site

NASA Astrophysics Data System (ADS)

Akob, D.; Bohu, T.; Beyer, A.; Schäffner, F.; Händel, M.; Johnson, C.; Merten, D.; Büchel, G.; Totsche, K.; Küsel, K.

2012-04-01

Uranium mining near Ronneburg, Germany resulted in widespread environmental contamination with acid mine drainage (AMD) and high concentrations of heavy metals and radionuclides. Despite physical remediation of the area, groundwater is still a source of heavy metal contaminants, e.g., Cd, Ni, Co, Cu and Zn, to nearby ecosystems. However, natural attenuation of heavy metals is occurring in Mn oxide rich soils and sediments ranging in pH from 5 to 7. While microorganisms readily oxidize Mn(II) and precipitate Mn oxides at pH ~7 under oxic conditions, few studies describe Mn(II)-oxidizing bacteria (MOB) at pH ~5 and/or in the presence of heavy metals. In this study we (1) isolated MOB from the contaminated Ronneburg area at pH 5.5 and 7 and (2) evaluated the biological formation of Mn oxides. We isolated nine MOB strains at pH 7 (members of the Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes phyla) and a single isolate at pH 5.5 (Oxalobacteraceae isolate AB_14, within the β-Proteobacteria). LA-ICP-MS showed that all isolates accumulated Mn and Fe in their biomass. However, the Oxalobacteraceae isolate AB_14 oxidizes more Mn without additional Fe in the medium. Preliminary FTIR analysis indicated that all isolates formed precipitates, which showed absorption bands that were characteristic for birnessite. High resolution TEM showed variable morphology of precipitates and EDS confirmed the presence of Mn oxides. Isolate AB_14 was not surrounded with precipitates whereas our Actinobacteria isolate AB_18 was encrusted with Mn oxides. Electron diffraction is currently being used to confirm the presence of birnessite and other Mn oxide phases. This, the first known report of any organism capable of Mn oxidation at low pH, demonstrated that MOB can be involved in the natural attenuation of both moderately acidic and neutral pH soils and sediments via the formation of biogenic Mn oxides. Future work will fully evaluate the minerals formed in this process as well as their interactions with contaminating heavy metals and radionuclides.

Role of Al in Zn bath on the formation of the inhibition layer during hot-dip galvanizing for a 1.2Si-1.5Mn transformation-induced plasticity steel

NASA Astrophysics Data System (ADS)

Wang, Kuang-Kuo; Hsu, Chiung-Wen; Chang, Liuwen; Gan, Dershin; Yang, Kuo-Cheng

2013-11-01

This study investigated the interaction between the Al in the Zn bath and the surface oxides formed by selective oxidation on a 1.2Si-1.5Mn TRIP steel during hot-dip galvanizing. XPS and TEM were employed for characterization. The results indicated that the amorphous xMnO·SiO2 oxide could react with Al to form a Si-Mn-Al-containing oxide. The crystalline MnSiO3 and Mn2SiO4 oxides could be largely reduced by Al to form holes in the oxide film. Consequently, the steel covered by a layer of mixed xMnO·SiO2 and MnSiO3 could form a continuous Fe2Al5 inhibition layer and showed the highest galvanizability among the three samples examined.

Authigenesis of trace metals in energetic tropical shelf environments

USGS Publications Warehouse

Breckel, E.J.; Emerson, S.; Balistrieri, L.S.

2005-01-01

We evaluated authigenic changes of Fe, Mn, V, U, Mo, Cd and Re in suboxic, periodically remobilized, tropical shelf sediments from the Amazon continental shelf and the Gulf of Papua. The Cd/Al, Mo/Al, and U/Al ratios in Amazon shelf sediments were 82%, 37%, and 16% less than those in Amazon River suspended sediments, respectively. Very large depletions of U previously reported in this environment were not observed. The Cd/Al ratios in Gulf of Papua sediments were 76% lower than measurements made on several Papua New Guinea rivers, whereas U/Al ratios in the shelf sediments were enriched by approximately 20%. Other metal/Al ratios in the Papua New Guinea river suspended sediments and continental shelf sediments were not distinguishably different. Comparison of metal/Al ratios to grain size distributions in Gulf of Papua samples indicates that our observations cannot be attributed to differences in grain size between the river suspended sediments and continental shelf sediments. These two shelves constitute a source of dissolved Cd to the world ocean equal to 29-100% of the dissolved Cd input from rivers, but only 3% of the dissolved Mo input and 4% of the dissolved U input. Release of Cd, Mo, and U in tropical shelf sediments is likely a result of intense Fe and Mn oxide reduction in pore waters and resuspension of the sediments. Since we do not observe depletions of particulate Fe and Mn in the shelf sediments most of these dissolved metals must reoxidize in the overlying waters and reprecipitate. As Cd exhibits the largest losses on these tropical shelves, we examined the ability of newly formed Fe and Mn oxides to adsorb dissolved Cd using a geochemical diffuse double-layer surface complexation model and found the oxide surfaces are relatively ineffective at readsorbing Cd in seawater due to surface-site competition by Mg and Ca. If the remobilization and reoxidation of Fe and Mn occurs frequently enough before sediment is buried significant amounts of Cd may be removed from the oxide surfaces. Because a much greater percentage of Mn than Fe becomes remobilized in these shelf sediments, metals closely associated with Mn oxides (like Cd) are more likely to show losses during deposition. ?? 2005 Elsevier Ltd. All rights reserved.

Structure and magnetic properties of Fe12X clusters

NASA Astrophysics Data System (ADS)

Gutsev, G. L.; Johnson, L. E.; Belay, K. G.; Weatherford, C. A.; Gutsev, L. G.; Ramachandran, B. R.

2014-02-01

The electronic and geometrical structures of a Fe12X family of binary clusters Fe12Al, Fe12Sc, Fe12Ti, Fe12V, Fe12Cr, Fe12Mn, Fe12Co, Fe12Ni, Fe12Cu, Fe12Zn, Fe12Y, Fe12Zr, Fe12Nb, Fe12Mo, Fe12Tc, Fe12Ru, Fe12Rh, Fe12Pd, Fe12Ag, Fe12Cd, and Fe12Gd are studied using density functional theory within generalized gradient approximation. It is found that the geometrical structures corresponding to the lowest total energy states found for the Fe12X clusters possess icosahedral shape with the substituent atom occupying the central or a surface site. The only exception presents Fe12Nb where a squeezed cage structure is the energetically most favorable. The substitution of an atom in the Fe13 cluster results in the decrease of its total spin magnetic moment of 44 μB, except for Fe12Mn and Fe12Gd. The Fe12X clusters are more stable than the parent Fe13 cluster when X = Al, Sc, Ti, V, Co, Y, Zr, Nb, Mo, Tc, Ru, and Rh.

Adsorption of arsenite and selenite using an inorganic ion exchanger based on Fe-Mn hydrous oxide.

PubMed

Szlachta, Małgorzata; Gerda, Vasyl; Chubar, Natalia

2012-01-01

The adsorption behaviour and mechanism of As(III) and Se(IV) oxyanion uptake using a mixed inorganic adsorbent were studied. The novel adsorbent, based on Fe(III)-Mn(III) hydrous oxides and manganese(II) carbonate, was synthesised using a hydrothermal precipitation approach in the presence of urea. The inorganic ion exchanger exhibited a high selectivity and adsorptive capacity towards As(III) (up to 47.6 mg/g) and Se(IV) (up to 29.0 mg/g), even at low equilibrium concentration. Although pH effects were typical for anionic species (i.e., the adsorption decreased upon pH increase), Se(IV) was more sensitive to pH changes than As(III). The rates of adsorption of both oxyanions were high. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) studies showed that the ion exchange adsorption of both anions took place via OH(-) groups, mainly from Fe(III) but also Mn(III) hydrous oxides. MnCO(3) did not contribute directly to As(III) and Se(IV) removal. A higher adsorptive capacity of the developed material towards As(III) was partly due to partial As(III) oxidation during adsorption. Copyright © 2011 Elsevier Inc. All rights reserved.

Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury

PubMed Central

Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira

2013-01-01

Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Manganese-induced effects on cerebral trace element and nitric oxide of Hyline cocks.

PubMed

Liu, Xiaofei; Zuo, Nan; Guan, Huanan; Han, Chunran; Xu, Shi Wen

2013-08-01

Exposure to Manganese (Mn) is a common phenomenon due to its environmental pervasiveness. To investigate the Mn-induced toxicity on cerebral trace element levels and crucial nitric oxide parameters on brain of birds, 50-day-old male Hyline cocks were fed either a commercial diet or a Mn-supplemented diet containing 600, 900, 1,800 mg kg(-1). After being treated with Mn for 30, 60, and 90 days, the following were determined: the changes in contents of copper (Cu), iron (Fe), zinc (Zn), calcium (Ca), selenium (Se) in brain; inducible nitric oxide synthase-nitric oxide (iNOS-NO) system activity in brain; and histopathology and ultrastructure changes of cerebral cortex. The results showed that Mn was accumulated in brain and the content of Cu and Fe increased. However, the levels of Zn and Se decreased and the Ca content presented no obvious regularity. Exposure to Mn significantly elevated the content of NO and the expression of iNOS mRNA. Activity of total NO synthase (T NOS) and iNOS appeared with an increased tendency. These findings suggested that Mn exposure resulted in the imbalance of cerebral trace elements and influenced iNOS in the molecular level, which are possible underlying nervous system injury mechanisms induced by Mn exposure.

MnO2 Nanorods Intercalating Graphene Oxide/Polyaniline Ternary Composites for Robust High-Performance Supercapacitors

NASA Astrophysics Data System (ADS)

Han, Guangqiang; Liu, Yun; Zhang, Lingling; Kan, Erjun; Zhang, Shaopeng; Tang, Jian; Tang, Weihua

2014-04-01

New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ~20 nm are conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance reaching 512 F/g and outstanding cycling performance, with ~97% capacitance retained over 5000 cycles. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications.

Large enhancement of Blocking temperature by control of interfacial structures in Pt/NiFe/IrMn/MgO/Pt multilayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Xi; Wang, Shouguo, E-mail: sgwang@ustb.edu.cn; Han, Gang

2015-09-15

The Blocking temperature (T{sub B}) of Pt/NiFe/IrMn/MgO/Pt multilayers was greatly enhanced from far below room temperature (RT) to above RT by inserting 1 nm thick Mg layer at IrMn/MgO interface. Furthermore, the exchange bias field (H{sub eb}) was increased as well by the control of interfacial structures. The evidence for a significant fraction of Mn-O bonding at IrMn/MgO interface without Mg insertion layer was provided by X-ray photoelectron spectroscopy. The bonding between Mn and O can decrease the antiferromagnetism of IrMn film, leading to lower value of T{sub B} in Pt/NiFe/IrMn/MgO/Pt multilayers. Ultrathin Mg film inserted at IrMn/MgO interface actingmore » as an oxygen sinking layer can suppress the oxidation reactions between Mn and O and reduce the formation of Mn-O bonding greatly. The oxidation suppression results in the recovery of the antiferromagnetism of IrMn film, which can enhance T{sub B} and H{sub eb}. Furthermore, the high resolution transmission electron microscopy demonstrates that the Mg insertion layer can efficiently promote a high-quality MgO (200) texture. This study will enhance the understanding of physics in antiferromagnet-based spintronic devices.« less

Chemical transformations during aging of zerovalent iron nanoparticles in the presence of common groundwater dissolved constituents.

PubMed

Reinsch, Brian C; Forsberg, Brady; Penn, R Lee; Kim, Christopher S; Lowry, Gregory V

2010-05-01

Nanoscale zerovalent iron (NZVI) that was aged in simulated groundwater was evaluated for alterations in composition and speciation over 6 months to understand the possible transformations NZVI could undergo in natural waters. NZVI was exposed to 10 mN of various common groundwater anions (Cl(-), NO(3)(-), SO(4)(2-), HPO(4)(2-), and HCO(3)(-)) or to dissolved oxygen (saturated, approximately 9 mg/L). Fresh and exposed NZVI samples, along with Fe-oxide model compounds, were then analyzed using synchrotron radiation X-ray absorption spectroscopy (XAS) to yield both relative oxidation state, using the X-ray absorption near edge structure (XANES), and quantitative speciation information regarding the types and proportions of mineral species present, from analysis of the extended X-ray absorption fine structure (EXAFS). Over 1 month of aging the dissolved anions inhibited the oxidation of the NZVI to varying degrees. Aging for 6 months, however, resulted in average oxidation states that were similar to each other regardless of the anion used, except for nitrate. Nitrate passivated the NZVI surface such that even after 6 months of aging the particles retained nearly the same mineral and Fe(0) content as fresh NZVI. Linear least-squares combination fitting (LCF) of the EXAFS spectra for 1 month-aged samples indicated that the oxidized particles remain predominantly a binary phase system containing Fe(0) and Fe(3)O(4), while the 6 month aged samples contained additional mineral phases such as vivianite (Fe(3)(PO(4))(2).8H(2)O) and iron sulfate species, possibly schwertmannite (Fe(3+)(16)O(16)(OH,SO(4))(12-13).10-12H(2)O). The presence of these additional mineral species was confirmed using synchrotron-based X-ray diffraction (XRD). NZVI exposed to water saturated with dissolved oxygen showed a rapid (<24 h) loss of Fe(0) and evolved both magnetite and maghemite (gamma-Fe(2)O(3)) within the oxide layer. These findings have implications toward the eventual fate, transport, and toxicity of NZVI used for groundwater remediation.

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

DOE PAGES

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; ...

2017-07-21

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; Noël, Vincent; Fritsch, Emmanuel; Proux, Olivier; Olivi, Luca; Ploquin, Florian; Morin, Guillaume

2017-11-01

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopy at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. This latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.

RECOVERY OF URANIUM VALUES FROM URANIUM BEARING RAW MATERIALS

DOEpatents

Michal, E.J.; Porter, R.R.

1959-06-16

Uranium leaching from ground uranium-bearing raw materials using MnO/sub 2/ in H/sub 2/SO/sub 4/ is described. The MnO/sub 2/ oxidizes U to the leachable hexavalent state. The MnO/sub 2/ does not replace Fe normally added, because the Fe complexes P and catalyzes the MnO/sub 2/ reaction. Three examples of continuous processes are given, but batch operation is also possible. The use of MnO/sub 2/ makes possible recovery of very low U values. (T.R.H.)

Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater

USGS Publications Warehouse

Bau, M.; Koschinsky, A.; Dulski, P.; Hein, J.R.

1996-01-01

In order to evaluate details of the partitioning behaviours of Y, rare earth elements (REEs), and Ti between inorganic metal oxide surfaces and seawater, we studied the distribution of these elements in hydrogenetic marine ferromanganese (Fe-Mn) crusts from the Central Pacific Ocean. Nonphosphatized Fe-Mn crusts display shale-normalized rare earths and yttrium (REYSN) patterns (Y inserted between Dy and Ho) that are depleted in light REEs (LREEs) and which show negative anomalies for YSN, and positive anomalies for LaSN, EuSN, GdSN, and in most cases, CeSN. They show considerably smaller Y/ Ho ratios than seawater or common igneous and clastic rocks, indicating that Y and Ho are fractionated in the marine environment. Compared to P-poor crusts, REYSN patterns of phosphatized Fe-Mn crusts are similar, but yield pronounced positive YSN anomalies, stronger positive LaSN anomalies, and enrichment of the HREEs relative to the MREEs. The data suggest modification of REY during phosphatization and indicate that studies requiring primary REY distributions or isotopic ratios should be restricted to nonphosphatized (layers of) Fe-Mn crusts. Apparent bulk coefficients, KMD, describing trace metal partitioning between nonphosphatized hydrogenetic Fe-Mn crusts and seawater, are similar for Pr to Eu and decrease for Eu to Yb. Exceptionally high values of KCeD, which are similar to those of Ti, result from oxidative scavenging of Ce and support previous suggestions that Ce(IV) is a hydroxide-dominated element in seawater. Yttrium and Gd show lower KD values than their respective neighbours in the REY series. Results of modelling the exchange equilibrium between REY dissolved in seawater and REY sorbed on hydrous Fe-Mn oxides corroborate previous studies that suggested the surface complexation of REY can be approximated by their first hydroxide binding constant. Negative "anomalies" occur for stabilities of bulk surface complexes of Gd, La, and particularly Y. The differences in inorganic surface complex stability between Y and Ho and between Gd and its REE neighbours are similar to those shown by the stabilities of complexes with aminocarboxylic acids and are significantly larger than those shown by stabilities of complexes with carboxylic acids. Hence, sorption of Y and REEs onto hydrous Fe-Mn oxides may contribute significantly to the positive YSN and GdSN anomalies in seawater.

Iron and manganese oxide mineralization in the Pacific

USGS Publications Warehouse

Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F.T.; Bau, M.; Kang, J.-K.; Lubick, N.

1997-01-01

Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ΣREEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ΣREE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect the redox conditions of seawater. The concentration of elements in hydrogenetic Fe-Mn crusts depends on a wide variety of water column and crust surface characteristics, whereas concentration of elements in hydrothermal oxide deposits depends of the intensity of leaching, rock types leached, and precipitation of sulphides at depth in the hydrothermal system.

Preservation of water samples for arsenic(III/V) determinations: An evaluation of the literature and new analytical results

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Maest, A.S.

2004-01-01

Published literature on preservation procedures for stabilizing aqueous inorganic As(III/V) redox species contains discrepancies. This study critically evaluates published reports on As redox preservation and explains discrepancies in the literature. Synthetic laboratory preservation experiments and time stability experiments were conducted for natural water samples from several field sites. Any field collection procedure that filters out microorganisms, adds a reagent that prevents dissolved Fe and Mn oxidation and precipitation, and isolates the sample from solar radiation will preserve the As(III/V) ratio. Reagents that prevent Fe and Mn oxidation and precipitation include HCl, H 2SO4, and EDTA, although extremely high concentrations of EDTA are necessary for some water samples high in Fe. Photo-catalyzed Fe(III) reduction causes As(III) oxidation; however, storing the sample in the dark prevents photochemical reactions. Furthermore, the presence of Fe(II) or SO 4 inhibits the oxidation of As(III) by Fe(III) because of complexation reactions and competing reactions with free radicals. Consequently, fast abiotic As(III) oxidation reactions observed in the laboratory are not observed in natural water samples for one or more of the following reasons: (1) the As redox species have already stabilized, (2) most natural waters contain very low dissolved Fe(III) concentrations, (3) the As(III) oxidation caused by Fe(III) photoreduction is inhibited by Fe(II) or SO4.

Oxidation of phenolic acids by soil iron and manganese oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lehmann, R.G.; Cheng, H.H.; Harsh, J.B.

Phenolic acids are intermediary metabolites of many aromatic chemicals and may be involved in humus formation, allelopathy, and nutrient availability. Depending on their structures, six phenolic acids were shown to react at different rates with oxidized forms of Fe and Mn in a Palouse soil (fine-silty, mixed, mesic Pachic Ultic Haploxeroll). Increasing methoxy substitution on the aromatic ring of phenolic acids increased the reaction rate. Reaction rate was also increased for longer carboxyl-containing side chains. After 4 h reaction, little of the applied (10 mg kg/sup -1/ soil) p-hydroxybenzoic or p-coumaric acids had reacted, while 0 to 5, 70, 90,more » and 100% of the vanillic, ferulic, syringic, and sinapic acids, respectively, had reacted. After 72 h under conditions limiting microbial growth, none of the p-hydroxybenzoic, 30% of the p-coumaric, and 50% of the vanillic acids had reacted. The reaction was shown to be predominantly chemical, and not biological, since phenolic acid extractabilities were similar for Palouse soil and for Palouse soil pretreated with LiOBr to remove organic matter. When the Palouse soil was pretreated with a sodium dithionite-citrate solution to remove Fe and Mn oxides, none of the phenolic acids reacted after 1 h. The reaction of sinapic acid with Palouse soil was shown to produce Fe(II) and soluble Mn as reaction products. The reaction of phenolic acids with soil was thus shown to be an oxidation of the phenolic acids, coupled with a reduction of soil Fe and Mn oxides.« less

Cyclic Catalytic Upgrading of Chemical Species Using Metal Oxide Materials

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Rolfe, Sara L. (Inventor); Schutte, Erick J. (Inventor)

2013-01-01

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce(sub x)B(sub y)B'(sub z)B''O(sub gamma; wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Cyclic catalytic upgrading of chemical species using metal oxide materials

DOEpatents

White, James H; Schutte, Erick J; Rolfe, Sara L

2013-05-07

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having the following formulas: (a) Ce.sub.xB.sub.yB'.sub.zB''O.sub..delta., wherein B=Ba, Sr, Ca, or Zr; B'=Mn, Co, and/or Fe; B''=Cu; 0.01

Origin of stratiform sediment-hosted manganese carbonate ore deposits: Examples from Molango, Mexico, and TaoJiang, China

USGS Publications Warehouse

Okita, P.M.; Shanks, Wayne C.

1992-01-01

Carbonate and sulfide minerals from the Molango, Mexico, and TaoJiang, China, Mn deposits display similar and distinctive ??34S and ??13C patterns in intervals of manganese carbonate mineralization. ??13C-values for Mn-bearing carbonate range from -17.8 to +0.5??? (PDB), with the most negative values occurring in high-grade ore zones that are composed predominantly of rhodochrosite. In contrast, calcite from below, within and above Mn-carbonate zones at Molango has ??13C???0??? (PDB). Markedly negative ??13C data indicate that a large proportion of the carbon in Mn-carbonates was derived from organic matter oxidation. Diagenetic reactions using MnO2 and SO2-4 to oxidize sedimentary organic matter were the principle causes of such 12C enrichment. Pyrite content and sulfide ?? 34S-values also show distinctive variations. In unmineralized rocks, very negative ??34S-values (avg. < -21??? CDT) and abundant pyrite content suggest that pyrite formed from diagenetic, bacteriogenic sulfate reduction. In contrast, Mn-bearing horizons typically contain only trace amounts of pyrite (e.g., <0.5 wt% S with ??34S-values 34S-enriched, in some cases to nearly the value for contemporaneous seawater. 34S-enriched pyrite from the Mn-carbonate intervals indicates sulfide precipitation in an environment that underwent extensive SO2-4 reduction, and was largely a closed system with regard to exchange of sulfate and dissolved sulfide with normal seawater. The occasional occurrence of 34S-depleted pyrite within Mn-carbonate zones dominated by 34S-enriched pyrite is evidence that closed-system conditions were intermittent and limited to local pore waters and did not involve entire sedimentary basins. Mn-carbonate precipitation may have occluded porosity in the surficial sediments, thus establishing an effective barrier to SO2-4 exchange with overlying seawater. Similar isotopic and mineralogic characteristics from both the Molango and TaoJiang deposits, widely separated in geologic time and space, suggest they were formed similarly by MnO2 precipitation at the margins of dysaerobic to anoxic marine basins. Mn-carbonate formed predominantly by early-diagenetic reduction of Mn-oxides via oxidation of organic matter in near-surface sediments. In addition to MnCO3 precipitation, organic matter oxidation reactions resulted in oxidation of FeS to Fe-oxides such as magnetite, maghemite and hematite. The latter process explains anomalously low pyrite content and abundant Fe-oxide minerals in ore zones dominated by rhodochrosite. ?? 1992.

Nanostructured Iron and Manganese Oxide Electrode Materials for Lithium Batteries: Influence of Chemical and Physical Properties on Electrochemistry

NASA Astrophysics Data System (ADS)

Durham, Jessica L.

The widespread use of portable electronics and growing interest in electric and hybrid vehicles has generated a mass market for batteries with increased energy densities and enhanced electrochemical performance. In order to address a variety of applications, commercially fabricated secondary lithium-ion batteries employ transition metal oxide based electrodes, the most prominent of which include lithium nickel manganese cobalt oxide (LiNixMn yCo1-x-yO2), lithium iron phosphate (LiFePO4), and lithium manganese oxide (LiMn 2O4). Transition metal oxides are of particular interest as cathode materials due to their robust framework for lithium intercalation, potential for high energy density, and utilization of earth-abundant elements (i.e. iron and manganese) leading to decreased toxicity and cost-effective battery production on industrial scales. Specifically, this research focuses on MgFe2O4, AgxMn8O16, and AgFeO 2 transition metal oxides for use as electrode materials in lithium-based batteries. The electrode materials are prepared via co-precipitation, reflux, and hydrothermal methods and characterized by several techniques (XRD, SEM, BET, TGA, DSC, XPS, Raman, etc.). The low-temperature syntheses allowed for precise manipulation of structural, compositional, and/or functional properties of MgFe2O4, AgxMn8 O16, and AgFeO2 which have been shown to influence electrochemical behavior. In addition, advanced in situ and ex situ characterization techniques are employed to study the lithiation/de-lithiation process and establish valid redox mechanisms. With respect to both chemical and physical properties, the influence of MgFe2O4 particle size and morphology on electrochemical behavior was established using ex situ X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) imaging. Based on composition, tunneled AgxMn8O16 nanorods, prepared with distinct Ag+ contents and crystallite sizes, display dramatic differences in ion-transport kinetics due to structural defects which facilitate Li+ diffusion through the tunnel walls and intimate electrochemical connection of bundled nanorods. Finally, a one-pot synthesis provided a series of AgFeO2/gamma-Fe 2O3 or AgxFeOy composites which, at the lowest silver regime (Ag0.2FeO1.6 ), exhibit 2X higher capacity than stoichiometric AgFeO2 and over 3X greater capacity than nanocrystalline gamma-Fe2O 3 after 50 cycles. Notably, mechanical mixing of AgFeO2 and gamma-Fe2O3 powders to mimic a one-pot Ag0.2FeO 1.6 composite yields lower delivered capacity and energy density where the results demonstrate the advantages of the directly prepared composite with more intimate particle connectivity not achievable through mechanical mixing.

Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

PubMed

Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

2010-11-01

In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE).

Behavior of LiFe1-yMnyPO4/C cathode materials upon electrochemical lithium intercalation/deintercalation

NASA Astrophysics Data System (ADS)

Novikova, Svetlana; Yaroslavtsev, Sergey; Rusakov, Vyacheslav; Chekannikov, Andrey; Kulova, Tatiana; Skundin, Alexander; Yaroslavtsev, Andrey

2015-12-01

LiFe1-yMnyPO4/C (y = 0-0.3) nanocomposites are prepared by the sol-gel method, and their properties are characterized with the use of the XRD analysis, SEM, impedance spectroscopy, charge/discharge tests, and Mössbauer spectroscopy. The samples with a low manganese content, LiFe1-yMnyPO4 (y = 0.1, 0.2) are characterized by an increased conductivity. In LiFe1-yMnyPO4 (x = 0.1-0.3), electrochemical lithium deintercalation/intercalation proceeds in two stages which due to the subsequent oxidation/reduction of iron and manganese ions. The LiFe1-yMnyPO4/С (y = 0.1, 0.2) samples show enhanced charge/discharge capacity, especially, at high current density (for LiFe0.9Mn0.1PO4/C, the discharge capacity is equal to 142 and 55 mAh g-1 at a current density of 20 and 1600 mA g-1, respectively). Mn2+ ↔ Mn3+ transition in LiFe1-yMnyPO4 proceeds via the solid solutions formation under gradual changes in the potential. For LiFe0.7Mn0.3PO4, oxidation and reduction of iron ions follow the same scenario. According to the Mössbauer spectroscopy data, manganese is orderly distributed in LixFeIII1-yMnyPO4: iron contains not more than one manganese cation in its nearest neighborhood. Moreover, combination of the Mössbauer spectroscopy and X-ray analysis data indicates that, in the interval where solid solutions exist in LixFe0.7Mn0.3PO4, the regions with an inhomogeneous distribution of divalent and trivalent manganese ions are formed.

Cu-Mn-Fe alloys and Mn-rich amphiboles in ancient copper slags from the Jabal Samran area, Saudi Arabia: With synopsis on chemistry of Fe-Mn(III) oxyhydroxides in alteration zones

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.

Resonant Raman scattering background in XRF spectra of binary samples

NASA Astrophysics Data System (ADS)

Sánchez, Héctor Jorge; Leani, Juan José

2015-02-01

In x-ray fluorescence analysis, spectra present singular characteristics produced by the different scattering processes. When atoms are irradiated with incident energy lower and close to an absorption edge, scattering peaks appear due to an inelastic process known as resonant Raman scattering. In this work we present theoretical calculations of the resonant Raman scattering contributions to the background of x-ray fluorescence spectra of binary samples of current technological or biological interest. On one hand, a binary alloy of Fe with traces of Mn (Mn: 0.01%, Fe: 99.99%) was studied because of its importance in the stainless steels industries. On the second hand a pure sample of Ti with V traces (Ti: 99%, V: 1%) was analyzed due to the current relevance in medical applications. In order to perform the calculations the Shiraiwa and Fujino's model was used to calculate characteristic intensities and scattering interactions. This model makes certain assumptions and approximations to achieve the calculations, especially in the case of the geometrical conditions and the incident and take-off beams. For the binary sample studied in this work and the considered experimental conditions, the calculations show that the resonant Raman scattering background is significant under the fluorescent peak, affects the symmetry of the peaks and, depending on the concentrations, overcomes the enhancements contributions (secondary fluorescence).

Effect of iron content on the catalytic activity of Fe-MnOx electrodeposited films in water oxidation

NASA Astrophysics Data System (ADS)

Selinger, Elizabeth; Ryczko, Kevin; Lopinski, Gregory; Armandi, Marco; Bonelli, Barbara; Tamblyn, Isaac

We report on the experimental and computational optimization and characterization of an MnOx structure containing a small amount of Fe, used as a catalyst for the water oxidation reaction (WOR), the key limiting reaction in water splitting. MnOx materials are earth-abundant and known to be efficient for WOR, and the method of cathodically electrodepositing catalysts allows for quick synthesis and a homogeneous coverage of the substrate. We present an increase in WOR activity due to the presence of Fe in this MnOx catalyst structure. First, we explored the optimal range for Fe(NO3)3 concentration in an KMnO4 solution for electrodeposition and tested for WOR activity. The catalyst structure was then analyzed using FESEM, XPS, and a Kelvin probe. We then developed a computational model of this structure, using density functional theory to obtain adsorption energies, work functions, projected density of states, and Born-Oppenheimer molecular dynamics. In this theoretical framework, we explore how these observables change with respect to concentration of Fe, and compare the theoretical model with experiment. special acknowledgement to the Italian Cultural Centre of Durham scholarship program.

Cubic structure and canted antiferromagnetism of CaMn7O12 doped with trivalent cations (Fe, Al, Cr)

NASA Astrophysics Data System (ADS)

Motin Seikh, Md.; Caignaert, V.; Lebedev, O. I.; Raveau, B.

2014-02-01

In this study, we show the dramatic effect of the doping of the octahedral sites with M3+ cations (Fe3+, Al3+ and Cr3+) upon the structure and magnetism of the rhombohedral double perovskite CaMn7O12. In the oxides CaMn7-xMxO12, charge ordering between Mn3+ and Mn4+ octahedral sites is destroyed leading to the cubic structure (Im-3), whereas the initial magnetic properties (TN~90 K) have disappeared leading to canted antiferromagnetism (TN≈50-70 K) for small x values (x ~0.2-1). A spin glass like behaviour is also observed for larger values (x~1) in the case of Fe substitution.

Core-Shell Composite Fibers for High-Performance Flexible Supercapacitor Electrodes.

PubMed

Lu, Xiaoyan; Shen, Chen; Zhang, Zeyang; Barrios, Elizabeth; Zhai, Lei

2018-01-31

Core-shell nanofibers containing poly(acrylic acid) (PAA) and manganese oxide nanoparticles as the core and polypyrrole (PPy) as the shell were fabricated through electrospinning the solution of PAA and manganese ions (PAA/Mn 2+ ). The obtained nanofibers were stabilized by Fe 3+ through the interaction between Fe 3+ ions and carboxylate groups. Subsequent oxidation of Mn 2+ by KMnO 4 produced uniform manganese dioxide (MnO 2 ) nanoparticles in the fibers. A PPy shell was created on the fibers by immersing the fibers in a pyrrole solution where the Fe 3+ ions in the fiber polymerized the pyrrole on the fiber surfaces. In the MnO 2 @PAA/PPy core-shell composite fibers, MnO 2 nanoparticles function as high-capacity materials, while the PPy shell prevents the loss of MnO 2 during the charge/discharge process. Such a unique structure makes the composite fibers efficient electrode materials for supercapacitors. The gravimetric specific capacity of the MnO 2 @PAA/PPy core-shell composite fibers was 564 F/g based on cyclic voltammetry curves at 10 mV/s and 580 F/g based on galvanostatic charge/discharge studies at 5 A/g. The MnO 2 @PAA/PPy core-shell composite fibers also present stable cycling performance with 100% capacitance retention after 5000 cycles.

MnO2 Nanorods Intercalating Graphene Oxide/Polyaniline Ternary Composites for Robust High-Performance Supercapacitors

PubMed Central

Han, Guangqiang; Liu, Yun; Zhang, Lingling; Kan, Erjun; Zhang, Shaopeng; Tang, Jian; Tang, Weihua

2014-01-01

New ternary composites of MnO2 nanorods, polyaniline (PANI) and graphene oxide (GO) have been prepared by a two-step process. The 100 nm-long MnO2 nanorods with a diameter ~20 nm are conformably coated with PANI layers and fastened between GO layers. The MnO2 nanorods incorporated ternary composites electrode exhibits significantly increased specific capacitance than PANI/GO binary composite in supercapacitors. The ternary composite with 70% MnO2 exhibits a highest specific capacitance reaching 512 F/g and outstanding cycling performance, with ~97% capacitance retained over 5000 cycles. The ternary composite approach offers an effective solution to enhance the device performance of metal-oxide based supercapacitors for long cycling applications. PMID:24769835

One-pot hydrothermal synthesis, characterization, and electrochemical properties of rGO/MnFe2O4 nanocomposites

NASA Astrophysics Data System (ADS)

Kotutha, Isara; Swatsitang, Ekaphan; Meewassana, Worawat; Maensiri, Santi

2015-06-01

In this work, a simple facile route for preparing an rGO/MnFe2O4 nanocomposite through a one-pot hydrothermal approach was demonstrated. Graphite oxide (GO) was prepared from graphite powder by a modified Hummers method. Fe(NO3)2 • 9H2O and Mn(NO3)2 • H2O were used as the precursors for the preparation of the rGO/MnFe2O4 nanocomposite. The formation of the rGO/MnFe2O4 nanocomposite was confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and Rama spectroscopy (Raman). The specific surface area of the prepared composite obtained by Brunauer-Emmett-Teller (BET) analysis was lower than that of pure rGO but higher than that of pure MnFe2O4. Consequently, the electrochemical performance was investigated by using a three-electrode cell system in 6.0 M KOH. The results show that the specific capacitance was determined to be 190.3, 276.9, and 144.5 F/g at a scan rate of 10 mV/s, and 194.9, 274.6, and 134.4 F/g at a current density of 5.0 A/g for rGO, rGO/(5 mmol) MnFe2O4, and rGO/(10 mmol) MnFe2O4, respectively. These results suggest that the composite of MnFe2O4 nanoparticles on an rGO nanosheet can improve the capacitive behavior of the fabricated electrode, but the electrochemical properties are reduced when the MnFe2O4 concentration ratio is high.

Preparation and characterization of highly water-soluble magnetic Fe3O4 nanoparticles via surface double-layered self-assembly method of sodium alpha-olefin sulfonate

NASA Astrophysics Data System (ADS)

Li, Honghong; Qin, Li; Feng, Ying; Hu, Lihua; Zhou, Chunhua

2015-06-01

A kind of double-layered self-assembly sodium alpha-olefin sulfonate (AOS) capped Fe3O4 magnetic nanoparticles (Fe3O4-AOS-MN) with highly water-solubility was prepared by a wet co-precipitation method with a pH of 4.8. The resulting Fe3O4-AOS-MN could be dispersed into water to form stable magnetic fluid without other treatments. The result of X-ray diffraction (XRD) indicated that the Fe3O4-AOS-MN maintained original crystalline structure and exhibited a diameter of about 7.5 nm. The iron oxide phase of nanoparticles determined by Raman spectroscopy is Fe3O4. Transmission electron microscopy (TEM) analysis confirmed that the Fe3O4-AOS-MN with spherical morphology were uniformly dispersed in water. FT-IR spectroscopy (FT-IR) and thermo-gravimetric analysis (TGA) verified the successful preparation of Fe3O4-AOS-MN capped with double-layered self-assembled AOS. The corresponding capacities of monolayer chemical absorption and the second-layer self-assembly absorption were respectively 4.07 and 14.71 wt% of Fe3O4-MN, which were much lower than those of other surfactants. Vibrating sample magnetometer (VSM) test result showed Fe3O4-AOS-MN possessed superparamagnetic behavior with the saturation magnetization value of about 44.45 emu/g. The blocking temperature TB of Fe3O4-AOS-MN capped with double-layered AOS is 170 K.

Immobilization of iron- and manganese-oxidizing bacteria with a biofilm-forming bacterium for the effective removal of iron and manganese from groundwater.

PubMed

Li, Chunyan; Wang, Shuting; Du, Xiaopeng; Cheng, Xiaosong; Fu, Meng; Hou, Ning; Li, Dapeng

2016-11-01

In this study, three bacteria with high Fe- and Mn-oxidizing capabilities were isolated from groundwater well sludge and identified as Acinetobacter sp., Bacillus megaterium and Sphingobacterium sp. The maximum removal ratios of Fe and Mn (99.75% and 96.69%) were obtained by an optimal combination of the bacteria at a temperature of 20.15°C, pH 7.09 and an inoculum size of 2.08%. Four lab-scale biofilters were tested in parallel for the removal of iron and manganese ions from groundwater. The results indicated that the Fe/Mn removal ratios of biofilter R4, which was inoculated with iron- and manganese-oxidizing bacteria and a biofilm-forming bacterium, were approximately 95% for each metal during continuous operation and were better than the other biofilters. This study demonstrated that the biofilm-forming bacterium could promote the immobilization of the iron- and manganese-oxidizing bacteria on the biofilters and enhance the removal efficiency of iron and manganese ions from groundwater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evidence for a cool wind from the K2 dwarf in the detached binary V471 Tauri

NASA Technical Reports Server (NTRS)

Mullan, D. J.; Sion, E. M.; Bruhweiler, F. C.; Carpenter, K. G.

1989-01-01

Evidence for mass loss from the K2 dwarf in V471 Tauri is found in the form of discrete absorption features in lines of various elements (Mg, Fe, Cr, Mn) and ionization stages (Mg I, Mg II, Fe I, Fe II). Resonant Mg II absorption indicates a mass loss rate of at least 10 to the -11th solar masses per year. The wind appears to be cool (no more than a few times 10,000 K).

Recovery of Manganese Ore Tailings by High-Gradient Magnetic Separation and Hydrometallurgical Method

NASA Astrophysics Data System (ADS)

Zhang, Xiufeng; Tan, Xiumin; Yi, Yuejun; Liu, Weizao; Li, Chun

2017-11-01

With the depletion of high-grade manganese ores, Mn ore tailings are considered valuable secondary resources. In this study, a process combining high-gradient magnetic separation (HGMS) with hydrometallurgical methods is proposed to recycle fine-grained Mn tailings. The Mn tailings were treated by HGMS at 12,500 G to obtain a Mn concentrate of 30% Mn with the recovery efficiency of 64%. The Mn concentrate could be used in the ferromanganese industry. To recover Mn further, the nonmagnetic fraction was leached by SO2 in an H2SO4 solution. Hydrogen peroxide was added to the leachate to oxidize Fe2+ to Fe3+, and the solution pH was adjusted to 5.0-5.5 with ammonia to remove Al, Fe, and Si impurities. The purified solution was reacted with NH4HCO3, and a saleable product of MnCO3 with 97.9% purity was obtained. The combined process can be applied to Mn recovery from finely dispersed weakly magnetic Mn ores or tailings.

Theory and Application of Photoelectron Diffraction for Complex Oxide Systems

NASA Astrophysics Data System (ADS)

Chassé, Angelika; Chassé, Thomas

2018-06-01

X-ray photoelectron diffraction (XPD) has been used to investigate film structures and local sites of surface and dopant atoms in complex oxide materials. We have performed angular-resolved measurements of intensity distribution curves (ADCs) and patterns (ADPs) of elemental core level intensities from binary to quaternary mixed oxide samples and compared them to multiple-scattering cluster (MSC) calculations in order to derive information on structural models and related parameters. MSC calculations permitted to describe both bulk diffraction features of binary oxide MnO(001) and the thickness-dependence of the tetragonal distortion of epitaxial MnO films on Ag(001). XPD was further used to investigate the surface termination of perovskite SrTiO3 and BaTiO3 substrates in order to evaluate influence of different ex situ and in situ preparation procedures on the surface layers, which are crucial for quality of following film growth. Despite the similarity of local environments of Sr (Ba) and Ti atoms in the perovskite film structure an angular region in the ADCs was identified as a fingerprint with the help of MSC simulations which provided clear conclusions on the perovskite oxide surfaces. Dopant sites in quaternary perovskite manganites La1-xCaxMnO3, La1-xSrxMnO3, and La1-xCexMnO3 were studied with polar angle scans of the photoemission intensities of host and dopant atoms. Both direct comparison of experimental ADCs and to the simulations within MSC models confirm the occupation of A sites by the dopants and the structural quality of the complex oxide films.

Transformation of triclosan to 2,8-dichlorodibenzo-p-dioxin by iron and manganese oxides under near dry conditions.

PubMed

Ding, Jiafeng; Su, Mian; Wu, Cuiwei; Lin, Kunde

2015-08-01

Triclosan (TCS) is a broad-spectrum antibacterial agent widely used in household and personal care products and is frequently detected in the environment. Previous studies have shown that TCS could be converted to the more toxic compound 2,8-dichlorodibenzo-p-dioxins (2,8-DCDD) in photochemical reactions and incineration processes. In this study, we demonstrated the formation of 2,8-DCDD from the oxidation of TCS by α-FeOOH and a natural manganese oxides (MnOx) sand. Experiments at room temperature and under near dry conditions showed that Fe and Mn oxides readily catalyzed the conversion of TCS to 2,8-DCDD and other products. Approximately 5.5% of TCS was transformed to 2,8-DCDD by α-FeOOH in 45 d and a higher conversion percentage (6.7%) was observed for MnOx sand in 16d. However, the presence of water in the samples significantly inhibited the formation of 2,8-DCDD. Besides 2,8-DCDD, 2,4-dichlorphenol (2,4-DCP), 4-chlorobenzene-1,2-diol, 2-chloro-5-(2,4-dichlorophenoxy)benzene-1,4-diol, and 2-chloro-5-(2,4-dichlorophenoxy)-1,4-benzoquinone were identified in the reactions. The possible pathways for the formation of reaction products were proposed. This study suggests that Fe and Mn oxides-mediated transformation of TCS under near dry conditions might be another potential pathway for the formation of 2,8-DCDD in the natural environment. Copyright © 2015 Elsevier Ltd. All rights reserved.

An educational overview of the chemistry, biochemistry and therapeutic aspects of Mn porphyrins--From superoxide dismutation to H2O2-driven pathways.

PubMed

Batinic-Haberle, Ines; Tovmasyan, Artak; Spasojevic, Ivan

2015-08-01

Most of the SOD mimics thus far developed belong to the classes of Mn-(MnPs) and Fe porphyrins(FePs), Mn(III) salens, Mn(II) cyclic polyamines and metal salts. Due to their remarkable stability we have predominantly explored Mn porphyrins, aiming initially at mimicking kinetics and thermodynamics of the catalysis of O2(-) dismutation by SOD enzymes. Several MnPs are of potency similar to SOD enzymes. The in vivo bioavailability and toxicity of MnPs have been addressed also. Numerous in vitro and in vivo studies indicate their impressive therapeutic efficacy. Increasing insight into complex cellular redox biology has been accompanied by increasing awareness of complex redox chemistry of MnPs. During O2(-) dismutation process, the most powerful Mn porphyrin-based SOD mimics reduce and oxidize O2(-) with close to identical rate constants. MnPs reduce and oxidize other reactive species also (none of them specific to MnPs), acting as reductants (antioxidant) and pro-oxidants. Distinction must be made between the type of reactions of MnPs and the favorable therapeutic effects we observe; the latter may be of either anti- or pro-oxidative nature. H2O2/MnP mediated oxidation of protein thiols and its impact on cellular transcription seems to dominate redox biology of MnPs. It has been thus far demonstrated that the ability of MnPs to catalyze O2(-) dismutation parallels all other reactivities (such as ONOO(-) reduction) and in turn their therapeutic efficacies. Assuming that all diseases have in common the perturbation of cellular redox environment, developing SOD mimics still seems to be the appropriate strategy for the design of potent redox-active therapeutics. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Performance evaluation of several commercial alloys in a reducing environment

NASA Astrophysics Data System (ADS)

Liu, Y.

Several commercial alloys including Ebrite, Crofer 22 APU, Haynes 230 and Haynes 242, which are candidates for intermediate-temperature solid oxide fuel cell (SOFC) interconnect materials, were isothermally and cyclically oxidized at 900 °C in the reducing atmosphere of Ar + 5 vol.% H 2 + 3 vol.% H 2O corresponding to the SOFC anode environment. Results indicate that these alloys exhibited good scale spallation resistance with the Ni-base alloys possessing better oxidation resistance over the Fe-base alloys. Both Mn-Cr spinel and Cr 2O 3 were formed in the oxide scales of these alloys. For Crofer 22 APU and Haynes 242, a continuous protective MnO and Mn-Cr spinel layer formed outside on the inner layer of Cr 2O 3. The increase in scale ASR after longer-term thermal exposure in the reducing environment was relatively slower for the Ni-base alloys than for the Fe-base alloys.

Advance concepts for conversion of syngas to liquids. Quarterly progress report No. 4, July 30, 1995--October 29, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pei-Shing Eugene Dai; Petty, R.H.; Ingram, C.

Substitution of transition metals for either aluminum and/or phosphorus in the AlPO{sub 4}-11 framework is found to afford novel heterogeneous catalysts for liquid phase hydroxylation of phenol with hydrogen peroxide. AlPO{sub 4}-11 is more active than SAPO-11 and MgAPO-11 for phenol conversion to hydroquinone. The Bronsted acid sites of SAPO-11 and MgAPO-11 may promote the decomposition of hydrogen peroxide to water and oxygen, thus leading to lower phenol conversions. Substitution of divalent and trivalent metal cations, such as Fe, Co and Mn appears to significantly improve the conversion of phenol. The activity follows the order of FeAPO-11>FeMnAPO-11>CoAPO-11>MnAPO-11{much_gt}ALPO{sub 4}-11. FeAPO-11, FeMnAPO-11more » and AlPO{sub 4}-11 give similar product selectivities of about 1:1 hydroquitione (HQ) to catechol (CT). MnAPO-11 and CoAPO-11 favor the production of catechol, particularly at low conversions. FeAPO-11 and TS-1 (titanium silicate with MFI topology) are comparable for the phenol conversions with TS-1 giving higher selectivities toward hydroquinone. The external surfaces of the catalysts plays a significant role in these oxidation reactions. MeAPO molecular sieves may be complementary to the metal silicalite catalysts for the catalytic oxidations in the manufacture of fine chemicals.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Improved removal performance and mechanism investigation of papermaking wastewater treatment using manganese enhanced Fenton reaction.

PubMed

Wang, Yingcai; Wang, Can; Shi, Shuai; Fang, Shuai

2018-06-01

The effects of Mn(II) on Fenton system to treat papermaking wastewater and the mechanism of Mn(II) enhanced Fenton reaction were investigated in this study. The chemical oxygen demand (COD) removal efficiency was enhanced in the presence of Mn(II), which increased by 19% compared with that of the Fenton system alone. The pseudo-first order reaction kinetic rate constant of Mn(II)/Fenton system was 2.11 times higher than that of Fenton system. 67%-81% COD were removed with the increasing Mn(II) concentration from 0 to 0.8 g/L. COD removal efficiency was also enhanced in a wider pH range (3-7), which indicated the operation parameters of Fenton technology could be broadened to a milder condition. The study of the mechanism showed that Mn(II) participated in the oxidation and coagulation stages in Fenton system. In the oxidation stage, Mn(II) promotes the production of HO 2 •/ O 2 • - , then HO 2 •/ O 2 • - reacts with Fe(III) to accelerate the formation of Fe(II), and finally accelerates the production of HO•. Meantime MnMnO 3 and Fe(OH) 3 forms in the coagulation stage, facilitating the removal of suspended substances and a large amount of COD, which enhances the overall COD removal of papermaking wastewater. This study provided a detailed mechanism to improve practical applications of Fenton technology.

Effect of metal oxides and black carbon (soot) on SO[sub 2]/O[sub 2]/H[sub 2]O reaction systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chughtai, A.R.; Brooks, M.E.; Smith, D.M.

1993-08-01

Particulates of atmospheric interest, including soot, oxidized soot, and oxides of transition metals, [open quotes]fellow travelers[close quotes] in the combustion of solid or liquid fossil fuels, have been examined for their influence on the heterogeneous oxidation of S(IV) to S(VI), both with and without the presence of simulated solar radiation. Under all conditions, MnO[sub 2] has been found to be the most active of the materials in this study. Effectiveness for the oxidation of SO[sub 2] in the presence of oxygen and water vapor decreases in the order: MnO[sub 2] [much gt] V[sub 2]O[sub 5] > CuO > Fe[sub 2]O[submore » 3] > Al[sub 2]O[sub 3] > Soot > TiO[sub 2] = SiO[sub 2] (cab-o-sil) [approximately] ZnO > ozonized soot = blank. The oxidation of SO[sub 2] also was carried out in the presence of soot-MnO[sub 2], soot-V[sub 2]O[sub 5], and soot-Fe[sub 2]O[sub 3] mixtures. The respective sulfate yields were found to be significantly higher than those obtained under similar conditions for the individual substrates. Other combinations, such as MnO[sub 2]/V[sub 2]O[sub 5] and MnO[sub 2]/Fe[sub 2]O[sub 3], yielded sulfate at levels higher than those obtained by any of the transition metal oxides or other oxide mixtures used. The mixing ratio of 1:0.75 (wt/wt) in the MnO[sub 2]/V[sub 2]O[sub 5] mixture was found to be optimum. With this mixture the sulfate yield was nearly twice the amount obtained if only MnO[sub 2] was used and nearly four times the amount if V[sub 2]O[sub 5] was used alone. Extensive analyses of the optimum mixture, to detect any unique identity, were inconclusive. 49 refs., 9 figs.« less

Structural characterization of Co100-xFex nano-oxide layer

NASA Astrophysics Data System (ADS)

Endo, Hiroaki; Doi, Masaaki; Hasegawa, Naoya; Sahashi, Masashi

2006-04-01

For the structural characterization of a Co100-xFex nano-oxide layer (NOL), the exchange bias properties of the Co100-xFex-natural oxidized NOL in the specular spin-valve (SPSV) system were investigated. The exchange bias energy (Jex) increased monotonically with the increasing Fe content for the Co100-xFex-NOL. The enhancement of both the magnetoresistance ratio and the exchange bias field (Hex) was realized by increasing the Fe content in the Co100-xFex-NOL. It should be mentioned that Hex more than 800 Oe is obtained by the insertion of Co30Fe70-NOL, even in NOL-SPSV, which is a remarkably higher pinning field than that ever reported on IrMn-SV. This high exchange bias field is considered to be realized by the formation of an Fe-rich fcc phase at the interface of IrMn.

Structured mesoporous Mn, Fe, and Co oxides: Synthesis, physicochemical, and catalytic properties

NASA Astrophysics Data System (ADS)

Maerle, A. A.; Karakulina, A. A.; Rodionova, L. I.; Moskovskaya, I. F.; Dobryakova, I. V.; Egorov, A. V.; Romanovskii, B. V.

2014-02-01

Structured mesoporous Mn, Fe, and Co oxides are synthesized using "soft" and "hard" templates; the resulting materials are characterized by XRD, SEM, TEM, BET, and TG. It is shown that in the first case, the oxides have high surface areas of up to 450 m2/g that are preserved after calcination of the material up to 300°C. Even though, the surface area of the oxides prepared by the "hard-template" method does not exceed 100 m2/g; it is, however, thermally stable up to 500°C. Catalytic activity of mesoporous oxides in methanol conversion was found to depend on both the nature of the transition metal and the type of template used in synthesis.

High-temperature oxidation of aluminum electroplated Fe-Mn alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bernabai, U.; Felli, F.; Capuano, G.A.

1990-04-01

Austenitic Mn-Al alloys (20-32 W/O Mn, 7-10 Al, 2-3 Si, 1C) were found to have satisfactory oxidation resistance up to 950{degree}C under isothermal conditions in air. Surface enrichment of aluminum is a necessary condition for obtaining an almost pure alumina scale for uses at higher temperatures. Four different Mn-steels were Al-coated by the Capuano electroplating process. In all the steels there was an increase in the hot-oxidation resistance. The best results were obtained with steels containing both Al and Si, and this for temperatures up to 1,100{degree}C.

Accurate solid solution range of BiMnxFe3-xO6 and low temperature magnetism

NASA Astrophysics Data System (ADS)

Jiang, Pengfei; Yue, Mufei; Cong, Rihong; Gao, Wenliang; Yang, Tao

2017-11-01

BiMnxFe3-xO6 (x = 1) represents a new type of oxide structure containing Bi3+ and competing magnetic super-exchanges. In literature, multiple magnetic states were realized at low temperatures in BiMnFe2O6, and the hypothetical parent compounds (BiMn3O6, BiFe3O6) were predicted to be different in magnetism. Herein, we performed a careful study on the syntheses of BiMnxFe3-xO6 at ambient pressure, and the solid solution range was determined to be 0.9 ≤ x ≤ 1.3 by Rietveld refinements on high-quality powder X-ray diffraction data. Due to the very similar cationic size of Mn3+ and Fe3+, and possibly the structural rigidity, there was no significant structure change in the whole range of solid solution. The magnetic behavior of BiMnxFe3-xO6 (x = 1.2, 1.22, 1.26, 1.28 and 1.3) was generally similar to BiMnFe2O6, while the relative higher concentration of Mn3+ led to the decreasing of the antiferromagnetic ordering temperature.

On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

PubMed

Resende, S F; Oliveira, B S; Augusti, R

2018-06-21

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

Elucidation of the Conversion Reaction of CoMnFeO4 Nanoparticles in Lithium Ion Battery Anode via Operando Studies.

PubMed

Permien, Stefan; Indris, Sylvio; Hansen, Anna-Lena; Scheuermann, Marco; Zahn, Dirk; Schürmann, Ulrich; Neubüser, Gero; Kienle, Lorenz; Yegudin, Eugen; Bensch, Wolfgang

2016-06-22

Conversion reactions deliver much higher capacities than intercalation/deintercalation reactions of commercial Li ion batteries. However, the complex reaction pathways of conversion reactions occurring during Li uptake and release are not entirely understood, especially the irreversible capacity loss of Mn(III)-containing oxidic spinels. Here, we report for the first time on the electrochemical Li uptake and release of Co(II)Mn(III)Fe(III)O4 spinel nanoparticles and the conversion reaction mechanisms elucidated by combined operando X-ray diffraction, operando and ex-situ X-ray absorption spectroscopy, transmission electron microscopy, (7)Li NMR, and molecular dynamics simulation. The combination of these techniques enabled uncovering the pronounced electronic changes and structural alterations on different length scales in a unique way. The spinel nanoparticles undergo a successive phase transition into a mixed monoxide caused by a movement of the reduced cations from tetrahedral to octahedral positions. While the redox reactions Fe(3+) ↔ Fe(0) and Co(2+) ↔ Co(0) occur for many charge/discharge cycles, metallic Mn nanoparticles formed during the first discharge can only be oxidized to Mn(2+) during charge. This finding explains the partial capacity loss reported for Mn(III)-based spinels. Furthermore, the results of the investigations evidence that the reaction mechanisms on the nanoscale are very different from pathways of microcrystalline materials.

The economic pre-treatment of coal mine drainage water with caustic and ozone.

PubMed

Boyden, B H; Nador, L; Addleman, S; Jeston, L

2017-09-01

Coal mine drainage waters are low in pH with varying amounts of iron and manganese and are generally brackish. The Austar Coal Mine in NSW, Australia, sought alternatives to their current lime dosing as the pre-treatment before the downstream reverse osmosis plant. Undesirable operating aspects of the current system include manganese and gypsum scaling/fouling, the need for anti-scalants and reduced water recovery. Thirteen processes for acid mine drainage were initially considered. The preferred process of caustic and ozone for Mn(II) oxidation was pilot tested at up to 0.74 kL/hr at the mine site. Under proper conditions and no aeration, about 81 per cent of the Fe could be removed (initially at 156 mg/L) as green rust. Supplemental aeration followed first-order kinetics and allowed 99.9 per cent Fe(II) oxidation and removal but only with a hydraulic residence time of about 47 minutes. The addition of supplemental Cu catalyst improved Fe removal. Ozone applied after caustic was effective in stoichiometrically oxidising recalcitrant Mn(II) and any remaining Fe(II). Control of the ozonation was achieved using the oxidation reduction potential during oxidation of the Mn(II) species. The use of caustic, followed by ozone, proved economically comparable to the current lime pre-treatment.

Weathering and precipitation after meteorite impact of Ni, Cr, Fe, Ca and Mn in K-T boundary clays from Stevns Klint

NASA Astrophysics Data System (ADS)

Miyano, Yumiko; Yoshiasa, Akira; Tobase, Tsubasa; Isobe, Hiroshi; Hongu, Hidetomo; Okube, Maki; Nakatsuka, Akihiko; Sugiyama, Kazumasa

2016-05-01

Ni, Cr, Fe, Ca and Mn K-edge XANES and EXAFS spectra were measured on K-T boundary clays from Stevns Klint in Denmark. According to XANES spectra and EXAFS analyses, the local structures of Ni, Cr and Fe in K-T boundary clays is similar to Ni(OH)2, Cr2O3 and FeOOH, respectively. It is assumed that the Ni, Cr and Fe elements in impact related glasses is changing into stable hydrate and oxide by the weathering and diagenesis at the surface of the Earth. Ca in K-T boundary clays maintains the diopside-like structure. Local structure of Ca in K-T clays seems to keep information on the condition at meteorite impact. Mn has a local structure like MnCO3 with divalent state. It is assumed that the origin on low abundant of Mn in the Fe-group element in K-T clays was the consumption by life activity and the diffusion to other parts.

Recent advances on Fe- and Mn-based cathode materials for lithium and sodium ion batteries

NASA Astrophysics Data System (ADS)

Zhu, Xiaobo; Lin, Tongen; Manning, Eric; Zhang, Yuancheng; Yu, Mengmeng; Zuo, Bin; Wang, Lianzhou

2018-06-01

The ever-growing market of electrochemical energy storage impels the advances on cost-effective and environmentally friendly battery chemistries. Lithium-ion batteries (LIBs) are currently the most critical energy storage devices for a variety of applications, while sodium-ion batteries (SIBs) are expected to complement LIBs in large-scale applications. In respect to their constituent components, the cathode part is the most significant sector regarding weight fraction and cost. Therefore, the development of cathode materials based on Earth's abundant elements (Fe and Mn) largely determines the prospects of the batteries. Herein, we offer a comprehensive review of the up-to-date advances on Fe- and Mn-based cathode materials for LIBs and SIBs, highlighting some promising candidates, such as Li- and Mn-rich layered oxides, LiNi0.5Mn1.5O4, LiFe1-xMnxPO4, NaxFeyMn1-yO2, Na4MnFe2(PO4)(P2O7), and Prussian blue analogs. Also, challenges and prospects are discussed to direct the possible development of cost-effective and high-performance cathode materials for future rechargeable batteries.

Diffusion Behavior of Mn and Si Between Liquid Oxide Inclusions and Solid Iron-Based Alloy at 1473 K

NASA Astrophysics Data System (ADS)

Kim, Sun-Joong; Tago, Hanae; Kim, Kyung-Ho; Kitamura, Shin-ya; Shibata, Hiroyuki

2018-06-01

In order to clarify the changes in the composition of oxide inclusions in steel, the effect of the metal and oxide composition on the reaction between solid Fe-based alloys and liquid multi-component oxides was investigated using the diffusion couple method at 1473 K. The measured concentration gradients of Mn and Si in the metal indicated that Mn diffused into the metal from the oxide, while the diffusion of Si occurred in the opposite direction. In addition, the MnO content in the oxide decreased with heat treatment time, while the SiO2 content increased. The compositional changes in both phases indicated that the Mn content in the metal near the interface increased with heat treatment with decreasing MnO content in the oxide. Assuming local equilibrium at the interface, the calculated [Mn]2/[Si] ratio at the interface in equilibrium with the oxide increased with increases in the MnO/SiO2 ratio in the oxide. The difference in the [Mn]2/[Si] ratios between the interface and the metal matrix increased, which caused the diffusion of Mn and Si between the multi-component oxide and metal. By measuring the diffusion lengths of Mn and Si in the metal, the chemical diffusion coefficients of Mn and Si were obtained to calculate the composition changes in Mn and Si in the metal. The calculated changes in Mn and Si in the metal agreed with the experimental results.

Fe-Ca-phosphate, Fe-silicate, and Mn-oxide minerals in concretions from the Monterey Formation

USGS Publications Warehouse

Medrano, M.D.; Piper, D.Z.

1997-01-01

Concentrically zoned phosphatic-enriched concretions were collected at three sites from the Monterey Formation. The following minerals were identified: vivianite, lipscombite, rockbridgeite, leucophosphite, mitridatite, carbonate fluorapatite, nontronite, todorokite, and barite. The mineralogy of the concretions was slightly different at each of the three collection sites. None of the concretions contains all of the minerals, but the spatial distribution of minerals in individual concretions, overlapping mineralogies between different concretions, and the geochemical properties of the separate minerals suggest a paragenesis represented by the above order. Eh increased from the precipitation of vivianite to that of rockbridgeite/lipscombite. The precipitation of leucophosphite, then mitridatite, carbonate fluorapatite and todorokite/Fe-oxide indicates increasing pH. Concretion growth culminated with the precipitation of todorokite, a Mn oxide, and minor amounts of barite along microfractures. Conspicuously absent are Fe-sulfide and Mn-phosphate minerals. The concretions are hosted by finely laminated diatomite. The laminations exhibit little to no deformation around the concretions, requiring that the concretions formed after compaction. We interpret this sediment feature and the paragenesis as recording the evolving pore-water chemistry as the formation was uplifted into the fresh-ground-water zone.

Raman studies of nanocomposites catalysts: temperature and pressure effects of CeAl, CeMn and NiAl oxides

NASA Astrophysics Data System (ADS)

da Silva, Antonio N.; Neto, Antonio B. S.; Oliveira, Alcemira C.; Junior, Manoel C.; Junior, Jose A. L.; Freire, Paulo T. C.; Filho, Josué M.; Oliveira, Alcineia C.; Lang, Rossano

2018-06-01

High temperature and pressure effects on the physicochemical properties of binary oxides catalysts were investigated. The nanocomposites catalysts comprising of CeAl, CeMn and NiAl were characterized through various physicochemical techniques. A study of the temperature and pressure induced phenomena monitored by Raman spectroscopy was proposed and discussed. Spectral modifications of the Raman modes belonging to the CeMn suggest structural changes in the solid due to the MnO2 phase oxidation with increasing temperature. The thermal expansion and lattice anharmonicity effects were observed on CeMn due to lack of stability of the lattice vacancies. The CeAl and NiAl composites presented crystallographic stability at low temperatures however, undertake a phase transformation of NiO/Al2O3 into NiAl2O4, mostly without any deformation in its structure with increasing the temperature. It was also inferred that the binary oxides are more stables in comparison with monoxides. Detailed pressure-dependent Raman measurements of the T2g phonon mode of CeMn and NiAl revealed that the pressure contributes to modify bonds length and reduces the particles sizes of the solids. On the contrary, high pressure on CeAl sample improved the stability with addition of Al2O3 in the CeO2 lattice. The results then suggest a good stability of CeAl and NiAl composite catalysts at high pressure and low temperature and show how to prospect of tuning the catalysis for surface reactions entirely through in situ spectroscopic investigations means.

On the novel double perovskites A2Fe(Mn0.5W0.5)O6 (A= Ca, Sr, Ba). Structural evolution and magnetism from neutron diffraction data

NASA Astrophysics Data System (ADS)

García-Ramos, Crisanto A.; Larrégola, Sebastián; Retuerto, María; Fernández-Díaz, María Teresa; Krezhov, Kiril; Alonso, José Antonio

2018-06-01

New A2Fe(Mn0.5W0.5)O6 (A = Ca, Sr, Ba) double perovskite oxides have been prepared by ceramic techniques. X-ray diffraction (XRD) complemented with neutron powder diffraction (NPD) indicate a structural evolution from monoclinic (space group P21/n) for A = Ca to cubic (Fm-3m) for A = Sr and finally to hexagonal (P63/mmc) for A = Ba as the perovskite tolerance factor increases with the A2+ ionic size. The three oxides present different tilting schemes of the FeO6 and (Mn,W)O6 octahedra. NPD data also show evidence in all cases of a considerable anti-site disordering, involving the partial occupancy of Fe positions by Mn atoms, and vice-versa. Magnetic susceptibility data show magnetic transitions below 50 K characterized by a strong irreversibility between ZFC and FC susceptibility curves. The A = Ca perovskite shows a G-type magnetic structure, with weak ordered magnetic moments due to the mentioned antisite disordering. Interesting magnetostrictive effects are observed for the Sr perovskite below 10 K.

Million-fold electrical conductivity enhancement in Fe 2(DEBDC) versus Mn 2(DEBDC) (E = S, O)

DOE PAGES

Sun, Lei; Hendon, Christopher H.; Minier, Mikael A.; ...

2015-05-01

Reaction of FeCl 2 and H 4DSBDC (2,5-disulfhydrylbenzene-1,4-dicarboxylic acid) leads to the formation of Fe 2(DSBDC), an analogue of M 2(DOBDC) (MOF-74, DOBDC 4– = 2,5-dihydroxybenzene-1,4-dicarboxylate). The bulk electrical conductivity values of both Fe 2(DSBDC) and Fe 2(DOBDC) are ~6 orders of magnitude higher than those of the Mn 2+ analogues, Mn 2(DEBDC) (E = O, S). Because the metals are of the same formal oxidation state, the increase in conductivity is attributed to the loosely bound Fe 2+ β-spin electron. Lastly, these results provide important insight for the rational design of conductive metal–organic frameworks, highlighting in particular the advantagesmore » of iron for synthesizing such materials.« less

The metal oxide fraction of pelagic sediment in the equatorial North Pacific Ocean: A source of metals in ferromanganese nodules

USGS Publications Warehouse

Piper, D.Z.

1988-01-01

Pelagic sediment recovered at DOMES Site A in the equatorial North Pacific (151??W, 9?? 15???N) consists of a surface homogeneous layer, approximately 10 cm thick, overlying a strongly mottled layer that is lighter in color. The radiolarian composition of both units is Quaternary. In areas where this sediment was only a few centimeters thick, the underlying sediment was early Tertiary. Clay mineralogy and major oxide composition of the two Quaternary sediments are uniform. Their similarity to continental shale suggests that the sediment has a terrigenous source. Clay mineralogy and major oxide composition of the Tertiary sediment also are uniform, although they differ markedly from the Quarternary sediment. In contrast to the major oxides, concentrations of Mn, Co, Cu, and Ni soluble in hydroxylamine hydrochlorideacetic acid are strongly different in the surface and subsurface Quaternary sediment. Mn and Ni exhibit pronounced depletions in the subsurface sediment, Ni slightly more than Mn. Cu is also depleted in the subsurface sediment, but less than Mn. It is also depleted in the subsurface Tertiary sediment, whereas the Mn concentration remains high. Concentration of Co relative to Mn increases into the subsurface Quaternary sediment to a constant Co:Mn ratio of 3 ?? 10-2. The trivalent REE (the REE exclusive of Ce) and Fe exhibit little down-core variation. Distribution of elements in these sediments is closely related to their concentration in associated surface ferromanganese nodules. The nodules are of two distinct types: those from the area where the Quaternary sediment is relatively thick have ??-MnO2 as the dominant manganese mineral. The ratios of Ni:Mn, Cu:Mn, and Fe:Mn in these nodules approximate the corresponding ratios of the soluble fraction of surface sediment. Todorokite is the dominant mineral of nodules recovered from areas where the Quaternary sediment is thin. Relatively high Cu/Mn, Ni/Mn, and low Fe/Mn ratios of these nodules mirror differences between the soluble fraction of surface and subsurface Quaternary sediment. These compositional trends of sediment and nodules at DOMES Site A reflect a diagenetic origin for the todorokite nodules and a predominantly hydrogenous origin for the ??-MnO2 nodules. ?? 1988.

Steam Oxidation Behavior of Advanced Steels and Ni-Based Alloys at 800 °C

NASA Astrophysics Data System (ADS)

Dudziak, T.; Boroń, L.; Deodeshmukh, V.; Sobczak, J.; Sobczak, N.; Witkowska, M.; Ratuszek, W.; Chruściel, K.

2017-03-01

This publication studies the steam oxidation behavior of advanced steels (309S, 310S and HR3C) and Ni-based alloys (Haynes® 230®, alloy 263, alloy 617 and Haynes® 282®) exposed at 800 °C for 2000 h under 1 bar pressure, in a pure water steam system. The results revealed that all exposed materials showed relatively low weight gain, with no spallation of the oxide scale within the 2000 h of exposure. XRD analysis showed that Ni-based alloys developed an oxide scale consisting of four main phases: Cr2O3 (alloy 617, Haynes® 282®, alloy 263 and Haynes® 230®), MnCr2O4 (alloy 617, Haynes® 282® and Haynes® 230®), NiCr2O4 (alloy 617) and TiO2 (alloy 263, Haynes® 282®). In contrast, advanced steels showed the development of Cr2O3, MnCr2O4, Mn7SiO12, FeMn(SiO4) and SiO2 phases. The steel with the highest Cr content showed the formation of Fe3O4 and the thickest oxide scale.

Divergent assembly mechanisms of the manganese/iron cofactors in R2lox and R2c proteins.

PubMed

Kutin, Yuri; Srinivas, Vivek; Fritz, Matthieu; Kositzki, Ramona; Shafaat, Hannah S; Birrell, James; Bill, Eckhard; Haumann, Michael; Lubitz, Wolfgang; Högbom, Martin; Griese, Julia J; Cox, Nicholas

2016-09-01

A manganese/iron cofactor which performs multi-electron oxidative chemistry is found in two classes of ferritin-like proteins, the small subunit (R2) of class Ic ribonucleotide reductase (R2c) and the R2-like ligand-binding oxidase (R2lox). It is unclear how a heterodimeric Mn/Fe metallocofactor is assembled in these two related proteins as opposed to a homodimeric Fe/Fe cofactor, especially considering the structural similarity and proximity of the two metal-binding sites in both protein scaffolds and the similar first coordination sphere ligand preferences of Mn II and Fe II . Using EPR and Mössbauer spectroscopies as well as X-ray anomalous dispersion, we examined metal loading and cofactor activation of both proteins in vitro (in solution). We find divergent cofactor assembly mechanisms for the two systems. In both cases, excess Mn II promotes heterobimetallic cofactor assembly. In the absence of Fe II , R2c cooperatively binds Mn II at both metal sites, whereas R2lox does not readily bind Mn II at either site. Heterometallic cofactor assembly is favored at substoichiometric Fe II concentrations in R2lox. Fe II and Mn II likely bind to the protein in a stepwise fashion, with Fe II binding to site 2 initiating cofactor assembly. In R2c, however, heterometallic assembly is presumably achieved by the displacement of Mn II by Fe II at site 2. The divergent metal loading mechanisms are correlated with the putative in vivo functions of R2c and R2lox, and most likely with the intracellular Mn II /Fe II concentrations in the host organisms from which they were isolated. Copyright © 2016 Elsevier Inc. All rights reserved.

MnFe2O4-graphene oxide magnetic nanoparticles as a high-performance adsorbent for rare earth elements: Synthesis, isotherms, kinetics, thermodynamics and desorption.

PubMed

Ghobadi, Misagh; Gharabaghi, Mahdi; Abdollahi, Hadi; Boroumand, Zohreh; Moradian, Marzieh

2018-06-05

In recent decades, considerable amounts of rare earth elements have been used and then released into industrial wastewater, which caused serious environmental problems. In this work, in order to recycle rare earth cations (La 3+ and Ce 3+ ) from aqueous solutions, MnFe 2 O 4 -Graphene oxide magnetic nanoparticles were synthesized and after characterization studies, their adsorption isotherms, kinetics, thermodynamics and desorption were comprehensively investigated. Characterized was performed using XRD, FE-SEM, FT-IR, Raman spectroscopy, VSM, BET and DLS. REE adsorption on MnFe 2 O 4 -GO was studied for the first time in the present work and the maximum adsorption capacity at the optimum condition (room temperature and pH = 7) for La 3+ and Ce 3+ were 1001 and 982 mg/g respectively, and the reactions were completed within 20 min. In addition, the adsorption data were well matched with the Langmuir model and the adsorption kinetics were fitted with the pseudo-second order model. The thermodynamic parameters were calculated and the reactions were found to be endothermic and spontaneous. Moreover, the Dubinin-Radushkevich model predicted chemical ion-exchange adsorption. Desorption studies also demonstrated that MnFe 2 O 4 -GO can be regenerated for multiple reuses. Overall, high adsorption capacity, chemical stability, reusability, fast kinetics, easy magnetic separation, and simple synthesis method indicated that MnFe 2 O 4 -GO is a high-performance adsorbent for REE. Copyright © 2018. Published by Elsevier B.V.

Silicon induced Fe deficiency affects Fe, Mn, Cu and Zn distribution in rice (Oryza sativa L.) growth in calcareous conditions.

PubMed

Carrasco-Gil, Sandra; Rodríguez-Menéndez, Sara; Fernández, Beatriz; Pereiro, Rosario; de la Fuente, Vicenta; Hernandez-Apaolaza, Lourdes

2018-04-01

A protective effect by silicon in the amelioration of iron chlorosis has recently been proved for Strategy 1 species, at acidic pH. However in calcareous conditions, the Si effect on Fe acquisition and distribution is still unknown. In this work, the effect of Si on Fe, Mn, Cu and Zn distribution was studied in rice (Strategy 2 species) under Fe sufficiency and deficiency. Plants (+Si or-Si) were grown initially with Fe, and then Fe was removed from the nutrient solution. The plants were then analysed using a combined approach including LA-ICP-MS images for each element of interest, the analysis of the Fe and Si concentration at different cell layers of root and leaf cross sections by SEM-EDX, and determining the apoplastic Fe, total micronutrient concentration and oxidative stress indexes. A different Si effect was observed depending on plant Fe status. Under Fe sufficiency, Si supply increased Fe root plaque formation, decreasing Fe concentration inside the root and increasing the oxidative stress in the plants. Therefore, Fe acquisition strategies were activated, and Fe translocation rate to the aerial parts was increased, even under an optimal Fe supply. Under Fe deficiency, +Si plants absorbed Fe from the plaque more rapidly than -Si plants, due to the previous activation of Fe deficiency strategies during the growing period (+Fe + Si). Higher Fe plaque formation due to Si supply during the growing period reduced Fe uptake and could activate Fe deficiency strategies in rice, making it more efficient against Fe chlorosis alterations. Silicon influenced Mn and Cu distribution in root. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Mn cycling in marine biofilms: effect on the rate of localized corrosion.

PubMed

Dexter, S C; Xu, K; Luther, G L

2003-04-01

Microelectrodes of the Au-Hg amalgam type have been used together with square wave voltammetry to measure profiles of oxygen, peroxide, Fe, Mn and sulfur chemical species through the thickness of natural assemblage marine biofilms grown on stainless steel alloy Nitronic 50 (UNS S20910). The data show Mn+2 and peroxide together at locations where the dissolved oxygen concentration was low. Oxidized species of Fe were also found at some locations. Sulfur species (predominantly S-2) was often found at locations where the dissolved oxygen concentration was below the detectable limit. Confocal scanning laser microscopy was used to image the microbial assemblage at the locations of the chemical profile data. Organisms with a filamentous morphology were found in consortia with rod and coccoidal shaped microbes at locations where dissolved Mn and peroxide were measured. The filamentous forms were usually absent at locations where Mn was not detected. It is suggested that the filamentous organisms may be Mn metabolizers, and that peroxidatic Mn re-oxidation may be taking place within the biofilm.

Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material.

PubMed

Wang, Huibo; Gao, Rui; Li, Zhengyao; Sun, Limei; Hu, Zhongbo; Liu, Xiangfeng

2018-05-07

P2-type layered oxides based on the elements Fe and Mn have attracted great interest as sodium ion battery (SIB) cathode materials owing to their inexpensive metal constituents and high specific capacity. However, they suffer from rapid capacity fading and complicated phase transformations. In this study, we modulate the crystal structure and optimize the electrochemical performances of Na 0.67 Mn 0.5 Fe 0.5 O 2 by Al doping for Mn or Fe, respectively, and the roles of Al in the enhancement of the rate capability and cycling performance are unraveled. (1) The substitution of Al for Mn or Fe decreases the lattice parameters a and c but enlarges d spacing and lengthens Na-O bonds, which enhances Na + diffusion and rate capability especially for Na 0.67 Mn 0.5 Fe 0.47 Al 0.03 O 2 . (2) Al doping reduces the thickness of TMO 2 and strengthens TM-O/O-O bonding. This enhances the layered structure stability and the capacity retention. (3) Al doping mitigates Mn 3+ and Jahn-Teller distortion, mitigating the irreversible phase transition. (4) Al doping also alleviates the lattice volume variation and the structure strain. This further improves the stability of the layered structure and the cycling performances particularly in the case of Al doping for Fe. The in-depth insights into the roles of Al substitution might be also useful for designing high-performance cathode materials for SIBs through appropriate lattice doping.

Preparation of manganese(II), chromium(III) and ferric(III) oxides nanoparticles in situ metal citraconate complexes frameworks

NASA Astrophysics Data System (ADS)

Refat, Moamen S.

2014-12-01

The new reactions of some divalent and trivalent transition metal ions (Mn(II), Cr(III), and Fe(III)) with citraconic acid has been studied. The obtained results indicate the formation of citraconic acid compounds with molar ratio of metal to citraconic acid of 2:2 or 2:3 with general formulas Mn2(C5H4O4)2 or M2(C5H4O4)3ṡnH2O where n = 6 for Cr, and Fe(III). The thermal decomposition of the crystalline solid complexes was investigated. The IR spectra of citraconate suggested that the carboxylic groups are bidentatically bridging and chelating. In the course of decomposition the complexes are dehydrated and then decompose either directly to oxides in only one step or with intermediate formation of oxocarbonates. This proposal dealing the preparation of MnO2, Fe2O3 and Cr2O3 nanoparticles. The crystalline structure of oxide products were checked by X-ray powder diffraction (XRD), and the morphology of particles by scanning electron microscopy (SEM).

Mechanisms controlling Cu, Fe, Mn, and Co profiles in peat of the Filson Creek Fen, northeastern Minnesota

USGS Publications Warehouse

Walton-Day, K.; Filipek, L.H.; Papp, C.S.E.

1990-01-01

Filson Creek Fen, located in northeastern Minnesota, overlies a Cu-Ni sulfide deposit. A site in the fen was studied to evaluate the hydrogeochemical mechanisms governing the development of Fe, Mn, Co, and Cu profiles in the peat. At the study site, surface peat approximately 1 m thick is separated from the underlying mineralized bedrock by a 6-12 m thickness of lake and glaciofluvial sediments and till. Concentrations of Fe, Mn, Co, and Cu in peat and major elements in pore water delineate a shallow, relatively oxidized, Cu-rich zone overlying a deeper, reduced, Fe-, Mn-, and Co-rich zone within the peat. Sequential metal extractions from peat samples reveal that 40-55% of the Cu in the shallow zone is associated with organic material, whereas the remaining Cu is distributed between iron-oxide, sulfide, and residual fractions. Sixty to seventy percent of the Fe, Mn, and Co concentrated in the deeper zone occur in the residual phase. The metal profiles and associations probably result from non-steady-state input of metals and detritus into the fen during formation of the peat column. The enrichment of organic-associated Cu in the upper, oxidized zone represents a combination of Cu transported into the fen with detrital plant fragments and soluble Cu, derived from weathering of outcrop and subcrop of the mineral deposit, transported into the fen, and fixed onto organic matter in the peat. The variable stratigraphy of the peat indicates that weathering processes and surface vegetation have changed through time in the fen. The Fe, Mn, and Co maxima at the base of the peat are associated with a maximum in detrital matter content of the peat resulting from a transition between the underlying inorganic sedimentary environment to an organic sedimentary environment. The chemistry of sediments and ground water collected beneath the peat indicate that mobilization of metals from sulfide minerals in the buried mineral deposit or glacial deposits is minimal. Therefore, the primary source of Cu to the peat at the study site is outcrops and shallow subcrops of the mineral deposit adjacent to the fen. ?? 1990.

Effect of Fe-substitution on the structure and magnetism of single crystals Mn2-xFexBO4

NASA Astrophysics Data System (ADS)

Platunov, M. S.; Kazak, N. V.; Knyazev, Yu. V.; Bezmaternykh, L. N.; Moshkina, E. M.; Trigub, A. L.; Veligzhanin, A. A.; Zubavichus, Y. V.; Solovyov, L. A.; Velikanov, D. A.; Ovchinnikov, S. G.

2017-10-01

Single crystalline Mn2-xFexBO4 with x = 0.3, 0.5, 0.7 grown by the flux method have been studied by means of X-ray diffraction and X-ray absorption spectroscopy at both Mn and Fe K edges. The compounds were found to crystallize in an orthorhombic warwickite structure (sp. gr. Pnam). The lattice parameters change linearly with x thus obeying the Vegard's law. The Fe3+ substitution for Mn3+ has been deduced from the X-ray absorption near-edge structure (XANES) spectra. Two energy positions of the absorption edges have been observed in Mn K-edge XANES spectra indicating the presence of manganese in two different oxidation states. Extended X-ray absorption fine structure (EXAFS) analysis has shown the reduction of local structural distortions upon Fe substitution. The magnetization data have revealed a spin-glass transition at TSG = 11, 14 and 18 K for x = 0.3, 0.5 and 0.7, respectively.

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction

PubMed Central

Hansel, Colleen M.; Zeiner, Carolyn A.; Santelli, Cara M.; Webb, Samuel M.

2012-01-01

Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems. PMID:22802654

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction.

PubMed

Hansel, Colleen M; Zeiner, Carolyn A; Santelli, Cara M; Webb, Samuel M

2012-07-31

Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems.

High-resolution structural studies of ultra-thin magnetic, transition metal overlayers and two-dimensional transition metal oxides using synchrotron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kellar, S.A.

This thesis report the surface-structure determination of three, ultra-thin magnetic transition-metal films, Fe/Au(100), Mn/Ni(100), and Mn/Cu(100) using Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) and photoelectron holography. These structural studies are the first to use non-s initial states in the ARPEFS procedure. This thesis also reports an ARPEFS surface-structure determination of a two-dimensional transition-metal oxide, [(1 x 1)O/W(110)] x 12. The authors have analyzed the ARPFES signal from the Au 4f{sub 7/5} core level of the Au(1 ML)/Fe(15 ML)/Au(100) system. The analysis shows that the Fe grows layer by layer with one monolayer of gold, acting as a surfactant, remaining onmore » top of the growing Fe layers. These surface gold atoms sit in the four-fold hollow site, 1.67 {+-} 0.02 A above the iron surface. The grown Fe layer is very much like the bulk, bcc iron, with an interlayer spacing of 1.43 {+-} 0.03 A. Analysis of the Mn 3p ARPEFS signals from c(2 x 2)Mn/Ni(100) and c(2 x 2)Mn/Cu(100) shows that the Mn forms highly corrugated surface alloys. The corrugation of the Mn/Ni(100) and Mn/Cu(100) systems are 0.24 {+-} 0.02 A and 0.30 {+-} 0.04 A respectively. In both cases the Mn is sticking above the plane of the surface substrate atoms. For the Mn/Ni(100) system the first layer Ni is contracted 4% from the bulk value. The Mn/Cu(100) system shows bulk spacing for the substrate Cu. Photoelectron holography shows that the Mn/Ni interface is very abrupt with very little Mn leaking into the second layer, while the Mn/Cu(100) case has a significant amount of Mn leaking into the second layer. A new, five-element electrostatic electron lens was developed for hemispherical electron-energy analyzers. This lens system can be operated at constant transverse or constants angular magnification, and has been optimized for use with the very small photon-spot sizes. Improvements to the hemispherical electron-energy analyzer are also discussed.« less

A hydrogen-oxidizing, Fe(III)-reducing microorganism from the Great Bay estuary, New Hampshire

USGS Publications Warehouse

Caccavo, F.; Blakemore, R.P.; Lovley, D.R.

1992-01-01

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

Enhancement of arsenite removal using manganese oxide coupled with iron (III) trimesic

NASA Astrophysics Data System (ADS)

Phanthasri, Jakkapop; Khamdahsag, Pummarin; Jutaporn, Panitan; Sorachoti, Kwannapat; Wantala, Kitirote; Tanboonchuy, Visanu

2018-01-01

A simultaneous removal of As(III) was investigated on a mixture of manganese oxide based octahedral molecular sieves (K-OMS2) and iron-benzenetricarboxylate (Fe-BTC). As(III) removal was stimulated by an oxidation cooperated with adsorption process. K-OMS2 and Fe-BTC were separately synthesized and characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). K-OMS2 showed characters of pure cryptomelane phase, nanorod structure, and a mixed-valent manganese framework with the coexistence of Mn(IV) and Mn(III). As(III) was successfully oxidized to As(V) by K-OMS2 in a temperature range of 303-333 K. An intermediate adsorption of As(V) was carried out with Fe-BTC in the same batch. A maximum adsorption capacity, described by Langmuir isotherm model, was observed at 76.34 mg/g. With an As(III) initial concentration of 5 mg/L, when K-OMS2 and Fe-BTC were simultaneously introduced into the solution, the As(III) removal process was completed within 60 min. Thus, it shortened the process time compared to the case where K-OMS2 was added first, followed by the addition of Fe-BTC.

Effects of exogenous pyoverdines on Fe availability and their impacts on Mn(II) oxidation by Pseudomonas putida GB-1

PubMed Central

Lee, Sung-Woo; Parker, Dorothy L.; Geszvain, Kati; Tebo, Bradley M.

2014-01-01

Pseudomonas putida GB-1 is a Mn(II)-oxidizing bacterium that produces pyoverdine-type siderophores (PVDs), which facilitate the uptake of Fe(III) but also influence MnO2 formation. Recently, a non-ribosomal peptide synthetase mutant that does not synthesize PVD was described. Here we identified a gene encoding the PVDGB-1 (PVD produced by strain GB-1) uptake receptor (PputGB1_4082) of strain GB-1 and confirmed its function by in-frame mutagenesis. Growth and other physiological responses of these two mutants and of wild type were compared during cultivation in the presence of three chemically distinct sets of PVDs (siderotypes n°1, n°2, and n°4) derived from various pseudomonads. Under iron-limiting conditions, Fe(III) complexes of various siderotype n°1 PVDs (including PVDGB-1) allowed growth of wild type and the synthetase mutant, but not the receptor mutant, confirming that iron uptake with any tested siderotype n°1 PVD depended on PputGB1_4082. Fe(III) complexes of a siderotype n°2 PVD were not utilized by any strain and strongly induced PVD synthesis. In contrast, Fe(III) complexes of siderotype n°4 PVDs promoted the growth of all three strains and did not induce PVD synthesis by the wild type, implying these complexes were utilized for iron uptake independent of PputGB1_4082. These differing properties of the three PVD types provided a way to differentiate between effects on MnO2 formation that resulted from iron limitation and others that required participation of the PVDGB-1 receptor. Specifically, MnO2 production was inhibited by siderotype n°1 but not n°4 PVDs indicating PVD synthesis or PputGB1_4082 involvement rather than iron-limitation caused the inhibition. In contrast, iron limitation was sufficient to explain the inhibition of Mn(II) oxidation by siderotype n°2 PVDs. Collectively, our results provide insight into how competition for iron via siderophores influences growth, iron nutrition and MnO2 formation in more complex environmental systems. PMID:25009534

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

USGS Publications Warehouse

Brown, J.G.; Glynn, P.D.

2003-01-01

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Hierarchical CNFs/MnCo2O4.5 nanofibers as a highly active oxidase mimetic and its application in biosensing

NASA Astrophysics Data System (ADS)

Gao, Mu; Lu, Xiaofeng; Nie, Guangdi; Chi, Maoqiang; Wang, Ce

2017-12-01

Recently, much attention has been paid on the nanomaterial-based artificial enzymes due to their tunable catalytic activity, high stability and low cost compared to the natural enzymes. Different from the peroxidase mimics which have been studied for several decades, nanomaterials with oxidase-like property are burgeoning in the recent years. In this paper, hierarchical carbon nanofibers (CNFs)/MnCo2O4.5 nanofibers as efficient oxidase mimics are reported. The products are synthesized by an electrospinning technique and an electrochemcial deposition process in which the CNFs are used as the working electrode where MnCo2O4.5 nanosheets deposit on. The resulting binary metal oxide-based nanocomposites exhibit a good oxidase-like activity toward the oxidations of 3,3‧,5,5‧tetramethylbenzi-dine (TMB), 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium (ABTS) salt and o-phenylenediamine (OPD) without exogenous addition of H2O2. The system of CNFs/MnCo2O4.5-TMB can be used as a candidate to detect sulfite and ascorbic acid via a colorimetric method with a high sensitivity. This work provides the efficient utilization and potential applications of binary metal oxide-based nanocomposites with oxidase activities in biosensors and other biotechnologies.

Al-Mn CVD-FBR coating on P92 steel as protection against steam oxidation at 650 °C: TGA-MS study

NASA Astrophysics Data System (ADS)

Castañeda, S. I.; Pérez, F. J.

2018-02-01

The initial stages oxidation of the P92 ferritic/martensitic steel with and without Al-Mn coating at 650 °C in Ar+40%H2O for 240 h were investigated by mass spectrometry (MS) and thermogravimetric analysis (TGA). TGA-MS measurements were conducted in a closed steam loop. An Al-Mn coating was deposited on P92 steel at 580 °C for 2 h by chemical vapour deposition in a fluidized bed reactor (CVD-FBR). The coating as-deposited was treated in the same reactor at 700 °C in Ar for 2h, in order to produce aluminide phases that form the protective alumina layer (Al2O3) during oxidation. MS measurements at 650 °C of the Al-Mn/P92 sample for 200 h indicated the presence of (Al-Mn-Cr-Fe-O) volatile species of small intensity. Uncoated P92 steel oxidized under the same steam oxidation conditions emitted greater intensities of volatile species of Cr, Fe and Mo in comparison with intensities from coated steel. TGA measurements verified that the mass gained by the coated sample was up to 300 times lower than for uncoated P92 steel. The morphology, composition and structure of samples by Scanning Electron Microscopy SEM, Backscattered Electron (BSE) detection, X-ray Energy Dispersive Spectrometry (EDAX) and X-ray Diffraction (XRD) are described.

Coating magnetic CuFe2O4 nanoparticles with OMS-2 for enhanced degradation of organic pollutants via peroxymonosulfate activation

NASA Astrophysics Data System (ADS)

Ye, Peng; Wu, Deming; Wang, Manye; Wei, Yi; Xu, Aihua; Li, Xiaoxia

2018-01-01

A heterogeneous magnetic CuFe2O4@OMS-2 catalyst was fabricated through a facile solvent-free process using Mn(CH3COO)2 and KMnO4 in the presence of CuFe2O4. It was found that the BET surface area of OMS-2 as well as the ratio of low-valent manganese species significantly increased in the hybrid catalyst, due to interactions between CuFe2O4 and the precursor of amorphous manganese oxide. Acid Orange 7 (AO7) and other organic pollutants could be completely degraded by the CuFe2O4@OMS-2 catalyst within 30 min in the presence of peroxymonosulfate (PMS), while CuFe2O4 and OMS-2 showed no significant activity for the reaction. The hybrid catalyst also exhibited excellent long-term stability and could be easily recovered with the assistance of an external magnetic field. A possible degradation mechanism for the synergistic effects of different valent metal species and reactive radicals was proposed, which involved the electron transfer from Mn(III) or Mn(II) species to PMS with the generation of sulfate and hydroxyl radicals, and from AO7 and Cu(I) in CuFe2O4 to Mn(IV) and Mn(III) to reduce these Mn species.

Potentially toxic elements (PTEs) in soils from the surroundings of the Trans-Amazonian Highway, Brazil.

PubMed

de Souza, Edna Santos; Fernandes, Antonio Rodrigues; de Souza Braz, Anderson Martins; Sabino, Lorena Lira Leite; Alleoni, Luís Reynaldo Ferracciú

2015-01-01

The Trans-Amazonian Highway (TAH) is located in the northern region of Brazil, comprising a border region where agricultural, mining, and logging activities are the main activities responsible for fostering economic development, in addition to large hydroelectric plants. Such activities lead to environmental contamination by potentially toxic elements (PTEs). Environmental monitoring is only possible through the determination of element contents under natural conditions. Many extraction methods have been proposed to determine PTEs' bioavailability in the soil; however, there is no consensus about which extractor is most suitable. In this study, we determined the contents of PTEs in soils in the surroundings of TAH after mineral extraction with diethylenetriaminepentaacetic acid-triethanolamine (DTPA-TEA), Mehlich I, and Mehlich III solutions. Soil samples were collected in areas of natural vegetation in the vicinity of TAH in the state of Pará, Brazil. Chemical attributes and particle size were determined, besides concentrations of Fe, Al, Mn, and Ti by sulfuric acid digestion, Si after alkaline solution attack, and poorly crystalline Fe, Al, and "free" Fe oxides. Mehlich III solution extracted greater contents from Fe, Al, and Pb as compared to Mehlich I and DTPA-TEA and similar contents from Cd, Mn, Zn, and Cu. Significant correlations were found between concentrations of PTEs and the contents of Fe and Mn oxides as well as organic carbon and soil cation exchange capacity. Contents of Cu, Mn, Fe, and Zn by the three methods were positively correlated.

Acidity and Alkalinity in mine drainage: Practical considerations

USGS Publications Warehouse

Cravotta, III, Charles A.; Kirby, Carl S.

2004-01-01

In this paper, we emphasize that the Standard Method hot peroxide treatment procedure for acidity determination (hot acidity) directly measures net acidity or net alkalinity, but that more than one water-quality measure can be useful as a measure of the severity of acid mine drainage. We demonstrate that the hot acidity is related to the pH, alkalinity, and dissolved concentrations of Fe, Mn, and Al in fresh mine drainage. We show that the hot acidity accurately indicates the potential for pH to decrease to acidic values after complete oxidation of Fe and Mn, and it indicates the excess alkalinity or that required for neutralization of the sample. We show that the hot acidity method gives consistent, interpretable results on fresh or aged samples. Regional data for mine-drainage quality in Pennsylvania indicated the pH of fresh samples was predominantly acidic (pH 2.5 to 4) or near neutral (pH 6 to 7); approximately 25 percent of the samples had intermediate pH values. This bimodal frequency distribution of pH was distinctive for fully oxidized samples; oxidized samples had acidic or near-neutral pH, only. Samples that had nearneutral pH after oxidation had negative hot acidity; samples that had acidic pH after oxidation had positive hot acidity. Samples with comparable pH values had variable hot acidities owing to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. The hot acidity was comparable to net acidity computed on the basis of initial pH and concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity computed from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was comparable to that computed on the basis of aqueous species and FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the hot acidities were comparable for fresh and aged samples. Thus, meaningful “net” acidity can be determined from a measured hot acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. Together, these water-quality data can be useful for evaluating the potential for toxicity, corrosion, or encrustation and can be helpful for determining the appropriate remediation. By demonstrating the measurements on fresh and aged samples, we hope to encourage (1) consistent use of the hot peroxide treatment procedure for acidity determination and (2) consistent reporting of negative acidity values.

Effect of citric acid and rhizosphere bacteria on metal plaque formation and metal accumulation in reeds in synthetic acid mine drainage solution.

PubMed

Guo, Lin; Cutright, Teresa J

2014-06-01

Many of regions in the world have been affected by acid mine drainage (AMD). The study assessed the effect of rhizosphere bacteria and citric acid (CA) on the metal plaque formation and heavy metal uptake in Phragmites australis cultured in synthetic AMD solution. Mn and Al plaque were not formed, but Fe plaque which was mediated by rhizosphere iron oxidizing bacteria (Fe(II)OB) was observed on the root system of reeds. Fe plaque did not significantly influence the uptake of Fe, Al and Mn into tissues of reeds. CA significantly (p<0.01) inhibited the growth of Fe(II)OB and decreased the formation of Fe plaque. CA also significantly improved (p<0.05) the accumulation of Fe, Mn and Al in all the tissues of reeds. Roots and rhizomes were the main organs to store metals. The roots contained 0.08±0.01mg/g Mn, 2.39±0.26mg/g Fe and 0.19±0.02mg/g Al, while the shoots accumulated 0.04±0.00mg/g Mn, 0.20±0.01mg/g Fe, 0.11±0.00mg/g Al in reeds cultured in solution amended with 2.101g/l CA and without inoculation of rhizosphere bacteria. Copyright © 2014 Elsevier Inc. All rights reserved.

Alternative catalysts for low-temperature CO-oxidation

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Schryer, Jacqueline; Upchurch, Billy T.; Brown, David R.

1990-01-01

MnO sub x, Ag/MnO sub x, Cu/MnO sub x, Pt/MnO sub x, Ru/MnO sub x, Au/CeO sub x, and Au/Fe2O3 were synthesized and tested for CO oxidation activity in low concentrations of stoichiometric CO and O2 at 30 to 75 C. Catalytic activity was measured for periods as long as 18000 minutes. At 75 deg Au/MnO sub x is most active sustaining nearly 100 percent CO conversion for 10000 minutes. It also retains high activity at 50 and 30 C with negligible decay in activity. A direct comparison between an unpretreated 10 percent Au/MnO sub x catalyst and an optimized 19.5 percent Pt/SnO sub 2 (pretreated) catalyst shows that the Au/MnO sub x catalyst exhibits much higher catalytic activity and far superior decay characteristics. Other catalysts including Au/CeO sub x and Au/Fe2O3 also perform well. The Cu/MnO sub x exhibits a high initial activity which decays rapidly. After the decay period the activity remains very stable making Cu/MnO sub x a potential candidate for long-term applications such as CO2 lasers in space.

Biological Superoxide In Manganese Oxide Formation

NASA Astrophysics Data System (ADS)

Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

2011-12-01

Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

Emerging memories: resistive switching mechanisms and current status

NASA Astrophysics Data System (ADS)

Jeong, Doo Seok; Thomas, Reji; Katiyar, R. S.; Scott, J. F.; Kohlstedt, H.; Petraru, A.; Hwang, Cheol Seong

2012-07-01

The resistance switching behaviour of several materials has recently attracted considerable attention for its application in non-volatile memory (NVM) devices, popularly described as resistive random access memories (RRAMs). RRAM is a type of NVM that uses a material(s) that changes the resistance when a voltage is applied. Resistive switching phenomena have been observed in many oxides: (i) binary transition metal oxides (TMOs), e.g. TiO2, Cr2O3, FeOx and NiO; (ii) perovskite-type complex TMOs that are variously functional, paraelectric, ferroelectric, multiferroic and magnetic, e.g. (Ba,Sr)TiO3, Pb(Zrx Ti1-x)O3, BiFeO3 and PrxCa1-xMnO3 (iii) large band gap high-k dielectrics, e.g. Al2O3 and Gd2O3; (iv) graphene oxides. In the non-oxide category, higher chalcogenides are front runners, e.g. In2Se3 and In2Te3. Hence, the number of materials showing this technologically interesting behaviour for information storage is enormous. Resistive switching in these materials can form the basis for the next generation of NVM, i.e. RRAM, when current semiconductor memory technology reaches its limit in terms of density. RRAMs may be the high-density and low-cost NVMs of the future. A review on this topic is of importance to focus concentration on the most promising materials to accelerate application into the semiconductor industry. This review is a small effort to realize the ambitious goal of RRAMs. Its basic focus is on resistive switching in various materials with particular emphasis on binary TMOs. It also addresses the current understanding of resistive switching behaviour. Moreover, a brief comparison between RRAMs and memristors is included. The review ends with the current status of RRAMs in terms of stability, scalability and switching speed, which are three important aspects of integration onto semiconductors.

Microbially-induced Fe and Mn oxides in condensed pelagic sediments (Middle-Upper Jurassic, Western Sicily)

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.

Bacterial Disproportionation of Elemental Sulfur Coupled to Chemical Reduction of Iron or Manganese

PubMed Central

Thamdrup, Bo; Finster, Kai; Hansen, Jens Würgler; Bak, Friedhelm

1993-01-01

A new chemolithotrophic bacterial metabolism was discovered in anaerobic marine enrichment cultures. Cultures in defined medium with elemental sulfur (S0) and amorphous ferric hydroxide (FeOOH) as sole substrates showed intense formation of sulfate. Furthermore, precipitation of ferrous sulfide and pyrite was observed. The transformations were accompanied by growth of slightly curved, rod-shaped bacteria. The quantification of the products revealed that S0 was microbially disproportionated to sulfate and sulfide, as follows: 4S0 + 4H2O → SO42- + 3H2S + 2H+. Subsequent chemical reactions between the formed sulfide and the added FeOOH led to the observed precipitation of iron sulfides. Sulfate and iron sulfides were also produced when FeOOH was replaced by FeCO3. Further enrichment with manganese oxide, MnO2, instead of FeOOH yielded stable cultures which formed sulfate during concomitant reduction of MnO2 to Mn2+. Growth of small rod-shaped bacteria was observed. When incubated without MnO2, the culture did not grow but produced small amounts of SO42- and H2S at a ratio of 1:3, indicating again a disproportionation of S0. The observed microbial disproportionation of S0 only proceeds significantly in the presence of sulfide-scavenging agents such as iron and manganese compounds. The population density of bacteria capable of S0 disproportionation in the presence of FeOOH or MnO2 was high, > 104 cm-3 in coastal sediments. The metabolism offers an explanation for recent observations of anaerobic sulfide oxidation to sulfate in anoxic sediments. PMID:16348835

The metamorphosis of heterometallic trinuclear antiferromagnetic complexes into nano-sized superparamagnetic spinels.

PubMed

Vasylenko, Inna V; Gavrylenko, Konstiantyn S; Il'yin, Vladimir G; Golub, Vladimir; Goloverda, Galina; Kolesnichenko, Vladimir; Addison, Anthony W; Pavlishchuk, Vitaly V

2010-05-15

Thermal decomposition of the trinuclear heterometallic oxoacetates [Fe(2)M(μ(3)-O)(CH(3)COO)(6)(H(2)O)(3)] has been used as a single-precursor method for synthesis of the spinel-structured ternary oxides MFe(2)O(4) (M = Mn(II), Co(II), and Ni(II)). This facile process occurring at 320 °C results in the formation of nanocrystalline, (7-20 nm) highly pure stoichiometric ferrites in quantitative yield. The magnetic properties of these nanoparticulate ferrites were studied in the 10-300 K temperature range, revealing superparamagnetic behaviour for the Ni and Mn particles and ferromagnetic behavior for the Co ones at room temperature. Their blocking temperatures follow the order: CoFe(2)O(4) > MnFe(2)O(4) > NiFe(2)O(4).

Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

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.

Biomineral microstructures in ferromanganese nodules: evidence of the biological and abiogenous origin

NASA Astrophysics Data System (ADS)

Lysyuk, G. N.

2011-10-01

Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50-60 vol % of X-ray amorphous components. X-ray amorphous nanosizedMn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe2O3, 7.11 SiO2, 2.41 CaO, 17.90 TiO2, 1.74Na2O,1.73 A12O3,1.30 MgO, 1.25P2O5,1.25 SO3,0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K2O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodules is as follows (wt %): 48.35 MnO, 6.23 Fe2O3, 8.76 MgO, 5.05 A12O3, 4.45 SiO2, 3.63 NiO, 2.30 Na2O, 2.19 CuO, 1.31 CaO, and 0.68 K2O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10-20 μm in size were identified in ferromanganese nodules as well. The formation of native metals can be explained by their crystallization at highly reducing conditions maintained by organic matter.

Fayalite-silica association in unequilibrated ordinary chondrites: Evidence for aqueous alteration on a parent body

NASA Technical Reports Server (NTRS)

Wasson, John T.; Krot, Alexander N

1994-01-01

We report ten occurrences of high-fayalite (Fa56-99 mol%; four with Fa greater than 82 mol%) olivine in association with silica in type-3 ordinary chondrites. Pyroxene with high Fs contents is much less common; Fs contents do not exceed 66 mol%, and most maxima are less than 50 mol%. In those cases where the amount of fayalite is minor relative to that of silica, the fayalite forms a layer on the silica, and shows textural evidence of formation by reaction of silica with oxidized Fe; the latter seems to have resulted from reaction of metallic Fe-Ni with an oxidant, most likely H2O vapor. The fayalite is generally in contact with pyroxene (and, in one case, olivine) having a much lower Fe/(Fe + Mg) ratios, indicating that lattice diffusion has been minimal. Formation of fayalite from SiO2 explains the low Mg content of this olivine; the Mg was sequestered inside the lattices of mafic minerals and was thus inaccessible. In contrast, the moderately high Mn contents of the fayalite indicate that an appreciable fraction of the Mn in the precursor assemblage was accessible; it was probably sited in the matrix in the form of tiny, poorly crystallized oxide grains produced by nebular condensation at temperatures too low to permit diffusion into forsterite or enstatite. The reaction of SiO2 with FeO produced by oxidation (during metamorphism) of Fe-Ni can also account for fayalitic olivine associated with SiO2 microspherules in the fine-grained matrices of type-3 ordinary chondrites and, because matrix is SiO2 normative, for other occurrences of fayalite in matrix. The presence of Mn in the fayalitic rims on the olivine of carbonaceous chondrites does not require a nebular sign.

Mobility and fractionation of Fe, Pb and Zn in river sediments from a silver and base-metals mining area: Taxco, México.

PubMed

Espinosa, E; Armienta, M A

2007-08-01

The impact of mining wastes on both the concentration and environmental mobility of Zn, Pb and Fe was studied in a shallow river. The studied tributary of the Taxco river is located south of the historical Ag, Zn, Cu and Pb mining area of Taxco, about 150 km south of México City. Methodology included total concentration determinations and sequential extraction analyses of the operational defined fractions of sediments. Results indicated that Fe, Pb and Zn concentrations are up to 5, 100 and 390 times respectively, greater than regional background concentrations. Higher contents of Pb and Zn were observed in the rainy season versus the dry season, whereas Fe was lower in the rainy season. Zinc and lead increased downflow in the dry season, and did not show any trend during the rainy season. Speciation showed that Zn was mainly linked to the carbonatic fraction (25-39%), to the hydrous Fe/Mn oxides fraction (15-25%) and to the organic matter and sulfide fraction (14-48%); lead was mainly associated to the hydrous Fe/Mn oxides (49-59%) and residual (22-39%) fractions; finally, iron was contained mainly in the residual (65-78%) and the hydrous Fe/Mn oxides fraction (15%). Mobility decreased according to the relation: Zn > Pb > Fe. Sediments were classified as strongly polluted in zinc, strongly to very strongly polluted in Pb, and moderately to strongly polluted in iron. However, a low proportion of metals in the exchangeable fractions, indicates low bioavailability. Limestone presence played a very important role on Zn and Pb fractionation and environmental mobility. Results show the importance of including geological background in river pollution studies.

Petrology and Geochemistry of Lunar Regolith Particle 65903,16-7: Evidence for Extreme Reduction and Oxidation

NASA Technical Reports Server (NTRS)

Zeigler, R. A.; Jolliff, B. L.; Korotev, R. L.; Kremser, D. T.; Haskin, L. A.

2001-01-01

Apollo 16 particle 65903,16-7 is a magnesian, alkali-rich impact melt breccia. Low Fe/Mn and high phosphide/phosphate ratios are evidence of severe reduction during impact-melt cooling. Presence of carbonate and FeOOH is evidence for later oxidation. Additional information is contained in the original extended abstract.

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

NASA Astrophysics Data System (ADS)

Filippov, V. P.; Bateev, A. B.; Lauer, Yu. A.

2016-12-01

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350-360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α-Fe(Cr), α-Fe(Cu), α-Fe 2O3 and Fe 3O4 compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.

Characterization of bacterial diversity associated with deep sea ferromanganese nodules from the South China Sea.

PubMed

Zhang, De-Chao; Liu, Yan-Xia; Li, Xin-Zheng

2015-09-01

Deep sea ferromanganese (FeMn) nodules contain metallic mineral resources and have great economic potential. In this study, a combination of culture-dependent and culture-independent (16S rRNA genes clone library and pyrosequencing) methods was used to investigate the bacterial diversity in FeMn nodules from Jiaolong Seamount, the South China Sea. Eleven bacterial strains including some moderate thermophiles were isolated. The majority of strains belonged to the phylum Proteobacteria; one isolate belonged to the phylum Firmicutes. A total of 259 near full-length bacterial 16S rRNA gene sequences in a clone library and 67,079 valid reads obtained using pyrosequencing indicated that members of the Gammaproteobacteria dominated, with the most abundant bacterial genera being Pseudomonas and Alteromonas. Sequence analysis indicated the presence of many organisms whose closest relatives are known manganese oxidizers, iron reducers, hydrogen-oxidizing bacteria and methylotrophs. This is the first reported investigation of bacterial diversity associated with deep sea FeMn nodules from the South China Sea.

Manganese micro-nodules on ancient brick walls.

PubMed

López-Arce, P; García-Guinea, J; Fierro, J L G

2003-01-20

Romans, Jews, Arabs and Christians built the ancient city of Toledo (Spain) with bricks as the main construction material. Manganese micro-nodules (circa 2 microm in diameter) have grown under the external bio-film surface of the bricks. Recent anthropogenic activities such as industrial emissions, foundries, or traffic and housing pollution have further altered these old bricks. The energy-dispersive X-ray microanalyses (XPS) of micro-nodules show Al, Si, Ca, K, Fe and Mn, with some carbon species. Manganese atoms are present only as Mn(4+) and iron as Fe(3+) (FeOOH-Fe(2)O(3) mixtures). The large concentration of alga biomass of the River Tagus and the Torcón and Guajaraz reservoirs suggest manganese micro-nodules are formed either from water solutions rich in anthropogenic MnO(4)K in a reduction environment (from Mn(7+) to Mn(4+)) or by oxidation mechanisms from dissolved Mn(2+) (from Mn(2+) to Mn(4+)) linked to algae biofilm onto the ancient brick surfaces. Ancient wall surfaces were also studied by scanning electron microscopy (SEM-EDS) and X-ray diffraction (XRD). Chemical and biological analyses of the waters around Toledo are also analysed for possible sources of manganese. Manganese micro-nodules on ancient brick walls are good indicators of manganese pollution. Copyright 2002 Elsevier Science B.V.

Neutron-diffraction studies of the crystal structure and the color enhancement in γ-irradiated tourmaline

NASA Astrophysics Data System (ADS)

Maneewong, Apichate; Seong, Baek Seok; Shin, Eun Joo; Kim, Jeong Seog; Kajornrith, Varavuth

2016-01-01

Tourmaline gemstones have an extremely complex composition and show great variety in color. Most color centers are related to transition-metal ions. Oxidation/reduction of these ions is known to be related with the color enhancement of tourmaline caused by gamma-ray ( γ)-irradiation and/or thermal treatment. However, the current understanding of the microscopic structure of the color centers remains weak. In this work, γ-irradiation was performed on three types of tourmaline gemstones to enhance the colors of the gemstones: two pink from Afghanistan and one green from Nigeria. All three samples were irradiated at 600 and 800 kGy. Their crystal structural and chemical behaviors have been investigated by using a Rietveld refinement analysis of neutron diffraction data, Energy Dispersive X-ray Fluorescence (EDXRF), Ultraviolet-visible Spectroscopy (UV-Vis) and X-ray Photoelectron Spectroscopy (XPS), and the results were compared with data obtained for samples in the natural state. Pink tourmaline of a high number of Mn ions (T2, 0.24 wt%) showed significant improvement in the quality of the pink color (rubellite) after irradiation of 800 kGy while the pink tourmaline of low MnO content (T1, 0.08 wt%) showed color adulteration. Pink color enhancement in T2, responding to darker pink, was associated with increases in the two absorption bands, one peaking at 396 and the other at 522 nm, after irradiation. These absorption bands are ascribed to d-d transitions of divalent manganese. T1 with color enhancement due to oxidation of Mn2+ showed a slightly larger < Y- O> distance. The green tourmaline containing much higher amounts of both Mn (T3) and Fe ions, 2.59 wt% and 5.7 wt%, respectively, changed to a yellow color after irradiation at 800 kGy. The refined structural parameters of this sample revealed distortions in the Z site. The < Z- O> distance decreased from 2.033 to 2.0192 Å. In addition, the unit-cell parameter was decreased after irradiation. The color change in T3 is ascribed to a decrease in the absorption band's intensity in the red color region (600 ˜ 750 nm). XPS measurement results also supported that the relative ratios of the Fe2+/Fe3+ [Fe3+ (Fe2 p 3/2 711.2 and Fe2 p 1/2 724.3 eV), Fe2+ (Fe2 p 3/2 710.2 and Fe2 p 1/2 722.8 eV)] and Mn2+/Mn3+ [Mn2+ (Mn2 p 3/2 641.4 and Mn2 p 1/2 652.3 eV), Mn3+ (Mn2 p 3/2 641.9 and Mn2 p 1/2 653.3 eV)] peak intensities were decreased after irradiation.

Cobalt-Free Permanent Magnet Alloys.

DTIC Science & Technology

1984-10-01

carbide co- UC CbC lumbium carbide M003 Uranium carbide - tho- UC 2 25ThC rium carbide ZrO2 MgO WOs Use of this Process for MnAlC As indicated in the...cobalt. Free World Cobal Consumption Estimated Breakdown by End Uses Magnetic alloys 20% Cemented carbides - 5% 30 SuPerolloy _ 15% Other steels and...would normally result in the formation of binary alloy of TbFe 2 and preventing the formation of amorphous alloy (Fe-B) contain- ing Tb. The

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

PubMed Central

Sahu, Sumit; Goldberg, David P.

2016-01-01

The rational design of well-defined, first-row transition metal complexes that can activate dioxygen has been a challenging goal for the synthetic inorganic chemist. The activation of O2 is important in part because of its central role in the functioning of metalloenzymes, which utilize O2 to perform a number of challenging reactions including the highly selective oxidation of various substrates. There is also great interest in utilizing O2, an abundant and environmentally benign oxidant, in synthetic catalytic oxidation systems. This Perspective brings together recent examples of biomimetic Fe and Mn complexes that can activate O2 in heme or nonheme-type ligand environments. The use of oxidants such as hypervalent iodine (e.g., ArIO), peracids (e.g., m-CPBA), peroxides (e.g., H2O2) or even superoxide is a popular choice for accessing well-characterized metal–superoxo, metal–peroxo, or metal–oxo species, but the instances of biomimetic Fe/Mn complexes that react with dioxygen to yield such observable metal–oxygen species are surprisingly few. This Perspective focuses on mononuclear Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal–oxygen species, and/or oxidize biologically relevant substrates. Analysis of these examples reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process. PMID:27576170

Copper and cobalt mobility in soil and accumulation in a metallophyte as influenced by experimental manipulation of soil chemical factors.

PubMed

Lange, Bastien; Pourret, Olivier; Meerts, Pierre; Jitaru, Petru; Cancès, Benjamin; Grison, Claude; Faucon, Michel-Pierre

2016-03-01

The influence of Fe oxides, Mn oxides and organic matter (OM) on the Cu and Co mobility in soil and accumulation in the metallophyte Anisopappus chinensis (Ac), as compared with Helianthus annuus (Ha), was experimentally investigated. Growth and accumulation response when increasing the exchangeable Cu and Co concentrations in soil were also investigated. Plants were cultivated on soil where concentrations of Cu, Co, Fe oxides, Mn oxides and OM content were varied according to 36 treatments. The OM supply decreased the Cu mobility and increased the Co mobility, resulting in decreasing the foliar Cu of Ac and increasing the foliar Co of Ha. The Fe oxides supply could increase the Cu accumulation for Ac, but was not verified for Ha. Compared with Ha, Ac increasingly accumulated Cu and Co without negative effect on plant growth while increasing Cu and Co mobility to phytotoxic concentrations. The results revealed promising perspectives for the use of Ac in Cu-contaminated environment phytoremediation applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Powder characteristics and biocidal activity of the MnOx-WO₃-TiO₂ system synthesized by a sol-gel method for antifouling agents.

PubMed

Shin, Byeongkil; Kim, Sangmin; Lee, Heesoo; Park, Hyun

2013-08-01

The TiO₂-system powders were investigated with respect to the crystallinity and the microstructure. The biocidal activity increased from TiO₂ to binary MnOx-TiO₂ to ternary MnOx-WO₃-TiO₂ against Vibrio fischeri as a model of Gram-negative bacteria. Anatase and rutile TiO₂ were not toxic even at 200 mg/L, but anatase has been observed in bacterial growth inhibition due to the different electronic band (lattice) structure. All materials containing manganese oxides were toxic: the toxicity correlation (EC₅₀) of MnOx-WO₃ and MnOx-WO₃-TiO₂ was 7.0, 1.8 ppm, respectively. The high antifouling activity of MnOx-WO₃-TiO₂ was attributed to its redox potential and soluble metal ions originating from tungsten oxides according to the improvements in the powder characteristics.

Effective surface modification of MnFe2O4@SiO2@PMIDA magnetic nanoparticles for rapid and high-density antibody immobilization

NASA Astrophysics Data System (ADS)

Rashid, Zahra; Soleimani, Masoud; Ghahremanzadeh, Ramin; Vossoughi, Manouchehr; Esmaeili, Elaheh

2017-12-01

The present study is aimed at the synthesis of MnFe2O4@SiO2@PMIDA in terms of highly efficient sensing platform for anti-prostate specific membrane antigen (PSMA) immobilization. Superparamagnetic manganese ferrite nanoparticles were synthesized following co-precipitation method and then SiO2 shell was coated on the magnetic core with tetraethyl orthosilicate (TEOS) through a silanization reaction to prevent oxidation, agglomeration and, increase the density of OH groups on the surface of MnFe2O4. Subsequently, MnFe2O4@SiO2@PMIDA obtained as a result of the reaction between N-(phosphonomethyl)iminodiacetic acid (PMIDA) and MnFe2O4@SiO2. The reactive carboxyl groups on the surface of magnetic nanoparticles can efficiently conjugate to a monoclonal antibody, specific to PSMA, which was confirmed by enzyme-linked immune sorbent assay (ELISA). Thus, this kind of functionalized magnetic nanoparticles is promising to be utilized in the improvement of ELISA-based biosensors and also will be effective in a variety of biomedical applications such as cell separation, diagnosis, and monitoring of human diseases.

Stable Water Oxidation in Acid Using Manganese-Modified TiO2 Protective Coatings.

PubMed

Siddiqi, Georges; Luo, Zhenya; Xie, Yujun; Pan, Zhenhua; Zhu, Qianhong; Röhr, Jason A; Cha, Judy J; Hu, Shu

2018-06-06

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O x , topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO 2 coatings, annealed (Ti,Mn)O x films can make direct charge transfer to a Fe(CN) 6 3-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN) 6 3-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO 2 . We correlated changes in the crystallinity (amorphous to rutile TiO 2 ) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.

Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel.

PubMed

Gund, Girish S; Dubal, Deepak P; Chodankar, Nilesh R; Cho, Jun Y; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D

2015-07-24

The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0-1 V and 0-2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg(-1), about 2-fold of higher energy density (41.8 Wh kg(-1)) than symmetric SC and excellent mechanical flexibility. Furthermore, the "real-life" demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC.

First Principles Study on the CO Oxidation on Mn-Embedded Divacancy Graphene

PubMed Central

Jiang, Quanguo; Zhang, Jianfeng; Ao, Zhimin; Huang, Huajie; He, Haiyan; Wu, Yuping

2018-01-01

The CO oxidation mechanism on graphene with divacancy (DG) embedded with transition metal from Sc to Zn has been studied by using first principles calculations. The results indicate that O2 molecule is preferentially adsorbed on Sc, Ti, V, Cr, Mn, and Fe-DG, which can avoid the CO poisoning problem that many catalysts facing and is beneficial to the CO oxidation progress. Further study indicates that Mn-DG shows the best catalytic properties for CO oxidation with consideration of both Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) oxidation mechanisms. Along the ER mechanism, the reaction energy barrier for the first step (CO free + O2 pre-adsorbed → OOCO) is 0.96 eV. Along the LH mechanism, the energy barrier for the rate limiting step (CO adsorbed + O2 adsorbed → OOCO) is only 0.41 eV, indicating that the CO oxidation on Mn-DG will occur along LH mechanism. The Hirshfeld charge distributions of O2 and CO molecules is tuned by the embedded Mn atom, and the charge transfer from the embedded Mn atom to the adsorbed molecules plays an important role for the CO oxidation. The result shows that the Mn-embedded divacancy graphene is a noble-metal free and efficient catalyst for CO oxidation at low temperature.

Removal of H 2S via an iron catalytic cycle and iron sulfide precipitation in the water column of dead end tributaries

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.

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.

Tuning electronic and magnetic properties of Mn-mullite oxide sub-nanoclusters via MnOn polyhedron units.

PubMed

Li, Hui; Cho, Kyeongjae; Li, Shunfang; Wang, Weichao

2018-06-13

Ternary oxide nano-clusters compared to unary metallic and binary ones potentially exhibit more remarkable properties due to their higher stoichiometric flexibility in addition to cluster size variations. Herein, by combining with the structural searching scheme CALYPSO, we have built a series of Mn-mullite oxide clusters (SmxMnyOz)n {(xyz) = (125); (115); n = 1-4, 8} prior to investigation of their geometric and electronic structures via first-principles calculations. In small size regime (n < 4), (SmxMnyOz)n prefer nonstoichiometric (Sm1Mn1O5)n phases composed of nonmagnetic MnO4 tetrahedrons. When n ≧ 4, the clusters tend to develop as stoichiometric (Sm1Mn2O5)n species, including magnetic MnOn polyhedrons and Mn-Mn dimers, which contribute 3d-orbitals (dz2 and/or dx2-y2) around the Fermi levels. The different magnetic behaviors of nonstoichiometric and stoichiometric species originate from the distinct couplings of MnOn polyhedronal units, wherein Mn atoms experience different ligand fields and thus display different spin states. Such findings enable the tuning of electronic properties and potential applications in heterogeneous catalysis, electrochemical catalysis, and the related fields via engineering cluster size and stoichiometry.

Speciations of trace metals in the Danube alluvial sediments within an oil refinery.

PubMed

Relić, Dubravka; Dordević, Dragana; Popović, Aleksandar; Blagojević, Tamara

2005-07-01

A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.

From dust to varnish: Geochemical constraints on rock varnish formation in the Negev Desert, Israel

NASA Astrophysics Data System (ADS)

Goldsmith, Yonaton; Stein, Mordechai; Enzel, Yehouda

2014-02-01

Chemical compositions of rock varnish from the Negev Desert of Israel and local settled dust were used to constrain the mechanisms of varnish formation and patterns of Mn enrichment and accumulation in the varnish. Rock varnish was sampled from coeval, undisturbed prehistoric flint artifacts along a south-north climatic transect (˜30-120 mm/yr of rain). Our analyses indicate that Mn, Ba and Pb in the varnish are significantly enriched (˜100×) in respect to the local settling dust and that Mn content systematically fluctuates with depth in the varnish. The varnish and settled dust data combined with basic thermodynamic and kinetic reasoning are used to constrain the following geochemical model of rock varnish formation: dust accumulates in micro-basins on exposed rock surfaces, under pH ˜8 (common Negev value) and during wetting by dew and rain, Mn in the dust is mobilized and leached to a depth of ˜5 μm under the varnish surface where Hollandite Mn-oxides precipitate and are adsorbed onto and between the porous clay minerals that comprise most of the varnish. During its mobile phase Mn-oxide is negatively charged and adsorbs rare earth elements. Once the solution dries abrasion removes the upper, weakly cemented dust sediment, which contains mainly Si, Al and Fe (which are not mobile at pH ˜8). Ca is also removed in large quantities. Mn, Ba, Pb and the REE are deposited at a depth and thus, protected from erosion. Reoccurrences of these processes result in a noticeable accumulation of these elements, but not of Si, Al or Fe. The alternating Mn-rich and Mn-poor laminas form as a result of a competition between the leaching rate of Mn and the adhesion rate of the clay minerals. When moisture is high (low), lamina with high (low) Mn/clay mineral ratio forms. The oxidation states involved in the varnish formation are unknown, therefore, to use Morgan's calculations we must assume, in agreement with the thermodynamic considerations (presented above), that during its varnish formation, Mn2+ is oxidized by one of the mechanisms presented by Morgan (2005). Morgan's data pertains to the rate in which Mn2+ is removed from the solution, and not to the rate of precipitation of Mn-oxides; the assumption used here is that the formation rate of Mn oxides is equal or faster than the removal rate of Mn2+, and therefore it is governed by the removal rate of Mn2+ from the solution. The efficiency of dissolution and deposition of Mn in varnish is unknown. Therefore, our calculations are based on full utilization (i.e., all Mn in the dust is transformed into Mn oxides in the varnish). Dust is abundant and its supply does not limit the process: this assumption is probably valid for deserts in general and more so to the central and southern Negev. Oxidation can occur only when moisture is available. The main moisture contributor to the Negev varnish is most likely dew (Goldsmith et al., 2012). To quantify the annual dew amounts, we used Zangvil (1996) data of an average of ˜1400 h/yr, which was measured over a six year period (at Sde Boker located between Divshon I and Nahal Boker in Fig. 1). For the following calculations, we used sites located in the central Negev, where it can be assumed that these sites experienced a similar moister regime as in Sde Boker. Morgan (2005) calculated the half-life for oxidation of Mn2+ in an aqueous environment. As stated above, these conditions prevail during ˜1400 h yr-1. With a Mn concentration in the dust of ˜500 ppm, the maximum amounts of Mn that would accumulate a year is: 35,000, 490, and 36 ppmMn yr-1 via bacterial oxidation, metal oxide catalysts, and homogenous solution oxidation, respectively.To estimate accumulation rates of Mn in the varnish, we calculated the total amount of Mn (MnTOT) in the measured profiles of the varnish by using an integral of the area under the graphs of [Mn]/depth (% atom/μm) (see appendix in Goldsmith, 2011). The MnTOT was divided by 9000 yr (the time interval since formation of the artifacts). The results (Table 3) indicate that the average Mn accumulation rates in the varnish range between 680 and 320 ppmMn yr-1. These accumulation rates are similar to the rates calculated by Morgan (2005) for oxidation via metal oxide catalysts (490 ppmMn yr-1). These rates are far below the Mn accumulation rates if bacteria oxidation was the primary process. Though, it is important to note that different bacteria might have lower oxidation rates, therefore, not completely eliminating the possible contribution of bacteria to the process.In the case of rock varnish, the major potential catalyst is clay minerals and not metal oxides. The adsorption of Mn on clay minerals was discussed by Garvie et al. (2008, Fig. 3) who state that “Nanometer-scale mixtures of Si- and Fe-rich material surrounded by Mn-rich material are common”. Clay minerals accelerate Mn(II) oxidation to a lesser degree than metal oxides (Wilson, 1980). Though, we have not identified in the literature rates of Mn adsorption on clay minerals to compare with the average Mn accumulation rates in the Negev varnish. This obstacle prevents drawing a firm conclusion based on oxidation rates alone. However, as a first order approximation, these estimations do point to a scenario of Mn accumulation via adsorption on a mixture of clay minerals and metal oxides. Rates associated with bacteria would have accumulated much larger amounts of Mn.

Oxic limestone drains for treatment of dilute, acidic mine drainage

USGS Publications Warehouse

Cravotta, Charles A.

1998-01-01

Limestone treatment systems can be effective for remediation of acidic mine drainage (AMD) that contains moderate concentrations of dissolved O2 , Fe3+ , or A13+ (1‐5 mg‐L‐1 ). Samples of water and limestone were collected periodically for 1 year at inflow, outflow, and intermediate points within underground, oxic limestone drains (OLDs) in Pennsylvania to evaluate the transport of dissolved metals and the effect of pH and Fe‐ and Al‐hydrolysis products on the rate of limestone dissolution. The influent was acidic and relatively dilute (pH <4; acidity < 90 mg‐L‐1 ) but contained 1‐4 mg‐L‐1 Of O2 , Fe3+ , A13+ , and Mn2+ . The total retention time in the OLDs ranged from 1.0 to 3.1 hours. Effluent remained oxic (02 >1 mg‐L‐1 ) but was near neutral (pH = 6.2‐7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and AI(OH)3, were visible as loosely bound, orange‐yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and AI(OH)3 particles were transported downflow. During the first 6 months of the experiment, Mn 2+ was transported conservatively through the OLDs; however, during the second 6 months, concentrations of Mn in effluent decreased by about 50% relative to influent. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of Mn as indicated by its enrichment relative to Fe in hydrous‐oxide particles and coatings on limestone. Despite thick (~1 mm) hydrous‐oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within the OLD where the limestone was not coated. The rate of limestone dissolution decreased with increased residence time, pH, and concentrations of Ca2+ and HCO3‐ and decreased PCO2. The following overall reaction shows alkalinity as an ultimate product of the iron hydrolysis reaction in an OLD:Fe2+ + 0.25 O2 +CaCO3 + 2.5 H2O --> Fe(OH)3 + 2 Ca2+ + 2 HCO3-where 2 moles of CaCO3 dissolve for each mole of Fe(OH)3 produced. Hence, in an OLD, rapidly dissolving limestone surfaces are not stable substrates for Fe(OH)3 attachment and armoring. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two‐stage treatment system consisting of an anoxic limestone drain an oxidation‐settling pond or wetland. To facilitate removal of hydrous‐oxide sludge, a perforated‐pipe subdrain can be installed within an OLD.

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

NASA Astrophysics Data System (ADS)

Aller, Robert C.; Rude, Peter D.

1988-03-01

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO 4- under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn +4 are apparently more effective than Mn +3 in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly aulolrophic CO 2 fixation. Lack of sensitivity to chlorate suggests that a No 3- reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O 2. Alkalinity is also simultaneously depeleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial Proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

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

The weathering of a sulfide orebody: Speciation and fate of some potential contaminants

USGS Publications Warehouse

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.

Effect of the nano-oxide layer as a Mn diffusion barrier in specular spin valves

NASA Astrophysics Data System (ADS)

Jang, S. H.; Kang, T.; Kim, H. J.; Kim, K. Y.

2002-07-01

In previous work an enhanced giant magnetoresistance (GMR) effect in spin valves (SVs) with a nano-oxide layer (NOL) after annealing at about 250-300 degC has been reported. We have shown that SVs with a NOL also have higher thermal stability of the MR ratio at 300 degC. From secondary-ion-mass spectroscopy and x-ray photoelectron spectroscopy depth profile analysis, the mechanism of the improved thermal stability of the SVs with a NOL is shown to be related to MnO formation within the NOL. Thus, Mn atoms from the FeMn layer are trapped, and Mn diffusion is inhibited by the NOL during annealing.

Fate of corrosion products released from stainless steel in marine sediments and seawater. Part 2. Sequim Bay clayey silt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, R.L.

1982-04-01

This report describes laboratory experiments in which neutron-activated 347 stainless steel specimens were exposed to clayey silt from Sequim Bay, Washington. The properties and trace metal geochemistry of the sediment and the amounts of corrosion products that were released under oxic and reduced conditions and their distribution among different chemical fractions of the sediment are discussed. The distributions of Cr, Mn, Fe, Ni and Cu among different chemical forms in the Sequim Bay sediment show that DTPA removed <10% of extractable Cr, Fe and Mn, approx. 20% of extractable Ni and approx. 30% of extractable Cu. The inorganic fraction (materialmore » soluble in 2.5% acetic acid) accounted for approx. 30% of total extractable Mn and approx. 10% or less of Cr, Fe, Ni and Cu. Major portions of Cr and Cu, and a large amount of Fe were in the organic fraction. Extractable Mn, Fe and Ni were associated with hydrous oxides likely as coatings on the mineral substrate of the sediment. No Co was detectable in any of the extracts. (PSB)« less

Evaluating the potential of three Fe- and Mn-(nano)oxides for the stabilization of Cd, Cu and Pb in contaminated soils.

PubMed

Michálková, Zuzana; Komárek, Michael; Šillerová, Hana; Della Puppa, Loïc; Joussein, Emmanuel; Bordas, François; Vaněk, Aleš; Vaněk, Ondřej; Ettler, Vojtěch

2014-12-15

The potential of three Fe- and Mn-(nano)oxides for stabilizing Cd, Cu and Pb in contaminated soils was investigated using batch and column experiments, adsorption tests and tests of soil microbial activity. A novel synthetic amorphous Mn oxide (AMO), which was recently proposed as a stabilizing amendment, proved to be the most efficient in decreasing the mobility of the studied metals compared to nano-maghemite and nano-magnetite. Its application resulted in significant decreases of exchangeable metal fractions (92%, 92% and 93% decreases of Cd, Cu and Pb concentrations, respectively). The adsorption capacity of the AMO was an order of magnitude higher than those recorded for the other amendments. It was also the most efficient treatment for reducing Cu concentrations in the soil solution. No negative effects on soil microorganisms were recorded. On the other hand, the AMO was able to dissolve soil organic matter to some extent. Copyright © 2014 Elsevier Ltd. All rights reserved.

Production and Isomeric Distribution of Xanthylium Cation Pigments and Their Precursors in Wine-like Conditions: Impact of Cu(II), Fe(II), Fe(III), Mn(II), Zn(II), and Al(III).

PubMed

Guo, Anque; Kontoudakis, Nikolaos; Scollary, Geoffrey R; Clark, Andrew C

2017-03-22

This study establishes the influence of Cu(II), Fe(II), Fe(III), Zn(II), Al(III), and Mn(II) on the oxidative production of xanthylium cations from (+)-catechin and either tartaric acid or glyoxylic acid in model wine systems. The reaction was studied at 25 °C using UHPLC and LC-HRMS for the analysis of phenolic products and their isomeric distribution. In addition to the expected products, a colorless product, tentatively assigned as a lactone, was detected for the first time. The results show the importance of Fe ions and a synergistic influence of Mn(II) in degrading tartaric acid to glyoxylic acid, whereas the other metal ions had minimal activity in this mechanistic step. Fe(II) and Fe(III) were shown to mediate the (+)-catechin-glyoxylic acid addition reaction, a role previously attributed to only Cu(II). Importantly, the study demonstrates that C-8 addition products of (+)-catechin are promoted by Cu(II), whereas C-6 addition products are promoted by Fe ions.

Oxide reduction during triggered-lightning fulgurite formation

NASA Astrophysics Data System (ADS)

Jones, B. E.; Jones, K. S.; Rambo, K. J.; Rakov, V. A.; Jerald, J.; Uman, M. A.

2005-03-01

In this study triggered-lightning induced fulgurites were formed in 99.9% pure binary oxides of manganese (MnO) and nickel (NiO) in order to study oxide reduction mechanisms. The fulgurite formation process involved packing the oxide in PVC holders and using the standard rocket-and-wire technique to trigger a lightning strike through the oxide at the International Center for Lightning Research and Testing in Camp Blanding, Florida. These two oxides were chosen from the thermodynamic extrapolation of the oxide stability using the Ellingham Diagram. This diagram indicates that NiO is significantly less stable than MnO. Fulgurites from the pure oxides were analyzed in a scanning electron microscope (SEM); secondary electron images, backscattered images and energy dispersive spectroscopy (EDS) were used to determine the microstructure and composition of the fulgurites. SEM/EDS analysis of the NiO and MnO prior to fulgurite formation confirmed they were pure binary oxides with no metallic contamination. After fulgurite formation, it was found that the nickel oxide fulgurite contained metallic nickel particles; the manganese oxide fulgurite showed no metallic phase formation. Transmission electron microscopy (TEM) examination confirmed that the MnO was a pure oxide with no sign of metallic phase formation. However, TEM results of the NiO showed that approximately 50% of the NiO was reduced to metallic face-centered cubic Ni. The Ni and NiO were observed to be coherent with the [1 0 0]Ni//[1 0 0]NiO and [1 1 0]Ni//[1 1 0]NiO. These results are consistent with the aforementioned thermodynamic stability calculations and show that the presence of carbonaceous material or mixtures of oxides is not necessary for oxide reduction during fulgurite formation. These studies do not rule out the possibility that electrolysis plays a role in oxide reduction. However, these fulgurites were made simultaneously during the same lightning strike and therefore were subjected to the same electrical current, and thus it is proposed the thermodynamic stability of the oxide must play a role in oxide reduction.

Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance

NASA Astrophysics Data System (ADS)

Cai, Sixiang; Hu, Hang; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

2016-02-01

Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts.Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts. Electronic supplementary information (ESI) available: Experimental details and catalytic performance of the Fe-Mn@CNTs IM, TEM images of Fe@Mn CNTs, stability and H2O resistance studies of the catalysts. See DOI: 10.1039/c5nr08701e

Structural, optical, dielectric and magnetic studies of gadolinium-added Mn-Cu nanoferrites

NASA Astrophysics Data System (ADS)

Kanna, R. Rajesh; Lenin, N.; Sakthipandi, K.; Kumar, A. Senthil

2018-05-01

Spinel ferrite with the general formula Mn1-xCuxFe1.85Gd0.15O4 (x = 0.2, 0.4, 0.6 and 0.8) was synthesized using the standard sonochemical method. The structure, optical, morphology, dielectric and magnetic properties of the prepared Mn1-xCuxFe1.85Gd0.15O4 nanoferrites were exhaustively investigated using various characterization techniques. The phase purity, secondary phase and crystallite parameters were studied from X-ray diffraction patterns. Fourier transform infrared spectra showed two absorption bands of transition metal oxides in the frequency range from 400 to 650 cm-1, which are related to asymmetric stretching modes of the spinel ferrites (AB2O4). Raman spectra have five active modes illustrating the vibration of O2- ions at both tetrahedral (A) site and octahedral (B) site ions. The wide and narrow scan spectrum from X-ray photoelectron spectroscopy results confirmed the presence of Mn, Cu, Gd, Fe, C and O elements in the composition. The oxidation state and core level of the photo electron peaks of Mn 2p, Cu 2p, Gd 3d, Fe 2p and O 1s were analyzed. The influence of the Cu2+ concentration in Mn1-xCuxFe1.85Gd0.15O4 on the morphology, varying from nanorods, nanoflakes to spherical, was explored on the basis of scanning electron microscopy images. Ultraviolet diffuse reflectance spectroscopy studies indicated that the optical bandgap (5.12-5.32 eV) of the nanoferrites showed an insulating behavior. The dielectric constant, loss tangent and complex dielectric constant values decreased with an increase in frequency with the addition of Gd3+ content. A vibrating sample magnetometer showed that the prepared nanoferrites had a soft ferromagnetic nature. The magnetic parameter changed markedly with an increase in the Cu content in Mn1-xCuxFe1.85Gd0.15O4 nanoferrites. The optical, dielectric and magnetic properties were considerably enhanced with the addition of Gd3+ ions in the spinel nanoferrites.

Low temperature processed MnCo2O4 and MnCo1.8Fe0.2O4 as effective protective coatings for solid oxide fuel cell interconnects at 750 °C

NASA Astrophysics Data System (ADS)

Molin, S.; Jasinski, P.; Mikkelsen, L.; Zhang, W.; Chen, M.; Hendriksen, P. V.

2016-12-01

In this study two materials, MnCo2O4 and MnCo1.8Fe0.2O4 are studied as potential protective coatings for Solid Oxide Fuel Cell interconnects working at 750 °C. First powder fabrication by a modified Pechini method is described followed by a description of the coating procedure. The protective action of the coating applied on Crofer 22 APU is evaluated by following the area specific resistance (ASR) of the scale/coating for 5500 h including several thermal cycles. The coating is prepared by brush painting and has a porous structure after deposition. Post mortem microstructural characterization performed on the coated samples shows good protection against chromium diffusion from the chromia scale ensured by a formation of a dense reaction layer. This study shows, that even without high temperature sintering and/or reactive sintering it is possible to fabricate protective coatings based on MnCo spinels.

Effect of Mn on the Formation of Oxide Buildups Upon HVOF-Sprayed MCrAlY-Ceramic-Type Cermet Coatings

NASA Astrophysics Data System (ADS)

Huang, Tsai-Shang

2011-03-01

Thermal spray coatings have been widely used on hearth rolls in a continuous annealing line to improve steel sheet quality and to prolong the roll service life. One of the common defects formed on a working hearth roll is the oxide buildup. HVOF-sprayed CoCrAlY-CrB2-Y2O3 coating was used in this study to duplicate buildups by reacting with Fe and Mn oxides. The reaction was performed in a furnace at 900 °C with inert gases flowing through. After reacting for 8 days, large Mn-rich buildups were formed on the coating while the buildups without Mn were very small. Mn was shown to enhance the formation of buildups. Buildups from a hearth roll were also examined and compared with the laboratory ones.

Effect of Fe-site Substitution on Pressure-induced Spin Transition in SrFeO2

NASA Astrophysics Data System (ADS)

Kawakami, Takateru; Yamamoto, Takafumi; Yata, Kanami; Ishii, Minoru; Watanabe, Yoshitaka; Mizumaki, Masaichiro; Kawamura, Naomi; Ishimatsu, Naoki; Takahashi, Hiroki; Okada, Taku; Yagi, Takehiko; Kageyama, Hiroshi

2017-12-01

The effect of Fe-site substitution on structural and physical properties of the infinite layer iron oxide SrFeO2 was investigated under high pressure by 57Fe Mössbauer spectroscopy, X-ray diffraction, X-ray absorption spectroscopy, X-ray magnetic circular dichroism, and electrical resistance measurements using a diamond-anvil cell. Both 20% Mn- and Co-substituted samples exhibit spin transitions from a high-spin (S = 2) to an intermediate-spin (S = 1) state at Pc ˜ 32 GPa, which is much the same pressure 33 GPa observed in SrFeO2. This result indicates that the spin transition pressure is insensitive to the d-orbital electron counts [Mn2+ (d5), Fe2+ (d6), Co2+ (d7)], but is governed by the local structure around the Fe site.

Novel carbon fiber cathode membrane with Fe/Mn/C/F/O elements in bio-electrochemical system (BES) to enhance wastewater treatment

NASA Astrophysics Data System (ADS)

Gao, Changfei; Liu, Lifen; Yang, Fenglin

2018-03-01

A novel conductive membrane with Fe/Mn/C/F/O elements is developed, it functions as the catalytic cathode of MFC and the antifouling filter of MBR simultaneously, in a newly designed integrated wastewater treatment system, without proton exchange membrane (PEM). The optimal conductive membrane is characterized using SEM-EDX, XRD and XPS. BET and porous structure analysis of the grounded membrane material indicate a narrow and small pore size (2-7 nm). The membrane surface is rich in Fe species (Fe - Fe2O3- Fe3O4) and manganese oxide (MnO2). Its characteristics such as excellent electro-chemical oxygen reduction reaction (ORR) activity, high clear water flux (>240 L/(m2·h)) and better antifouling filtration performance are further confirmed. The new system features bio-electrochemical system (BES) and integrates bio-filtration (trickling filter and air contact oxidation bed) and proton transfer through quartz sand chamber (QSC) which eliminates the use of expensive proton exchange membrane. The system removes chemical oxygen demand (>97.4%), ammonia nitrogen (>96.7%), total phosphorus (>98.0%) effectively, and it simultaneously generates electricity (446 mW/m3). The low cost and high performances, economic and advantageous system has good compatibility with existing wastewater treatment facilities and a wide application prospect.

Mixed Metal Oxides of the Type CoxZn1-xFe2O4 as Photocatalysts for Malachite Green Degradation Under UV Light Irradiation.

PubMed

Tzvetkov, Martin; Milanova, Maria; Cherkezova-Zheleva, Zara; Spassova, Ivanka; Valcheva, Evgenia; Zaharieva, Joana; Ivan, Mitov

2017-06-01

A combination of thermal and mechanical (high energy ball milling) treatment was applied in an attempt to obtain polycrystalline mixed metal binary and ternary oxides of the type CoxZn1-xFe2O4 (x = 0; 0.25; 0.5; 0.75; 1). The synthetic procedure used successfully produced single-phased, homogeneous ZnFe2O4, CoFe2O4, and Co0.75Zn0.25Fe2O4, as well as mixed oxides, whose composition depended both on the duration of the high energy ball milling and the ratio Zn(II)/Co(II). The formation of spinel-like structures was proved by XRD, Mössbauer spectroscopy and Raman spectroscopy. For the characterization of the samples low-temperature N2 adsorption, UV/Vis spectroscopy and transmission electron microscopy were applied. The energy band gap of the samples was calculated, suggesting they are promising photocatalysts. The decomposition of the Malachite Green in model water solutions under UV-light irradiation was successfully achieved in the presence of the samples as photocatalysts. The highest rate constant was obtained for the sample synthesized at longer milling time in combination with higher Zn(II)/Co(II) ratio. The photocatalytic activity of the ternary mixed oxides was compared with the pure hematite, α-Fe2O3, and the binary ZnFe2O4 and CoFe2O4 ferrites with spinel structure that were treated in the same way. A synergetic effect of α-Fe2O3 and the spinel-like structure on the photocatalytic properties of ternary mixed metal oxides was detected.

Large exchange bias induced by polycrystalline Mn3Ga antiferromagnetic films with controlled layer thickness

NASA Astrophysics Data System (ADS)

Wu, Haokaifeng; Sudoh, Iori; Xu, Ruihan; Si, Wenshuo; Vaz, C. A. F.; Kim, Jun-young; Vallejo-Fernandez, Gonzalo; Hirohata, Atsufumi

2018-05-01

Polycrystalline Mn3Ga layers with thickness in the range from 6–20 nm were deposited at room temperature by a high target utilisation sputtering. To investigate the onset of exchange-bias, a ferromagnetic Co0.6Fe0.4 layer (3.3–9 nm thick) capped with 5 nm Ta, were subsequently deposited. X-ray diffraction measurements confirm the presence of Mn3Ga (0 0 0 2) and (0 0 0 4) peaks characteristic of the D019 antiferromagnetic structure. The 6 nm thick Mn3Ga film shows the largest exchange bias of 430 Oe at 120 K with a blocking temperature of 225 K. The blocking temperature is found to decrease with increasing Mn3Ga thickness. These results in combination with x-ray reflectivity measurements confirm that the quality of the Mn3Ga/Co0.6Fe0.4 interface controls the exchange bias, with the sharp interface with the 6-nm-thick Mn3Ga inducing the largest exchange bias. The magneto-crystalline anisotropy for 6 nm thick Mn3Ga thin film sample is calculated to be . Such a binary antiferromagnetic Heusler alloy is compatible with the current memory fabrication process and hence has a great potential for antiferromagnetic spintronics.

Bimetal-organic frameworks for functionality optimization: MnFe-MOF-74 as a stable and efficient catalyst for the epoxidation of alkenes with H2O2.

PubMed

Yuan, Kuo; Song, Tianqun; Wang, Dawei; Zou, Ye; Li, Jinfeng; Zhang, Xiaotao; Tang, Zhiyong; Hu, Wenping

2018-01-25

In this work, we synthesized a series of microcrystalline Mn x N 100-x -MOF-74 (N = Fe, Co and Ni) materials by a one-pot reaction. Powder X-ray diffraction (PXRD) patterns of Mn x N 100-x -MOF-74 matched well with those of single-metal MOF-74, and the scanning electron microscopy (SEM) images exhibited homogeneous nanocrystallites aggregated together. The amounts and dispersion of metals were analyzed by using inductively coupled plasma (ICP) and energy-dispersive X-ray spectroscopy (EDS), separately. Mn x N 100-x -MOF-74 could remain crystalline and efficiently catalyze the epoxidation of alkenes in DMF with NaHCO 3 and 30% H 2 O 2 . In particular, Mn 29.39 Fe 70.61 -MOF-74 can achieve almost 100% conversion for styrene with 95.0% selectivity towards styrene oxide and be reused at least five times without loss of activity.

Pt-Au/MOx-CeO₂ (M = Mn, Fe, Ti) Catalysts for the Co-Oxidation of CO and H₂ at Room Temperature.

PubMed

Hong, Xiaowei; Sun, Ye; Zhu, Tianle; Liu, Zhiming

2017-02-27

A series of nanostructured Pt-Au/MO x -CeO₂ (M = Mn, Fe, Ti) catalysts were prepared and their catalytic performance for the co-oxidation of carbon monoxide (CO) and hydrogen (H₂) were evaluated at room temperature. The results showed that MO x promoted the CO oxidation of Pt-Au/CeO₂, but only the TiO₂ could enhance co-oxidation of CO and H₂ over Pt-Au/CeO₂. Related characterizations were conducted to clarify the promoting effect of MO x . Temperature-programmed reduction of hydrogen (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results suggested that MO x could improve the charge transfer from Au sites to CeO₂, resulting in a high concentration of Ce 3+ and cationic Au species which benefits for the CO oxidation. In-situ diffuse reflectance infrared Fourier transform spectroscopy (In-situ DRIFTS) results indicated that TiO₂ could facilitate the oxidation of H₂ over the Pt-Au/TiO₂-CeO₂ catalyst.

Fe3O4 and MnO2 assembled on honeycomb briquette cinders (HBC) for arsenic removal from aqueous solutions.

PubMed

Zhu, Jin; Baig, Shams Ali; Sheng, Tiantian; Lou, Zimo; Wang, Zhuoxing; Xu, Xinhua

2015-04-09

In this study, a novel composite adsorbent (HBC-Fe3O4-MnO2) was synthesized by combining honeycomb briquette cinders (HBC) with Fe3O4 and MnO2 through a co-precipitation process. The purpose was to make the best use of the oxidative property of MnO2 and the adsorptive ability of magnetic Fe3O4 for enhanced As(III) and As(V) removal from aqueous solutions. Experimental results showed that the adsorption capacity of As(III) was observed to be much higher than As(V). The maximum adsorption capacity (2.16 mg/g) was achieved for As(III) by using HBC-Fe3O4-MnO2 (3:2) as compared to HBC-Fe3O4-MnO2 (2:1) and HBC-Fe3O4-MnO2 (1:1). The experimental data of As(V) adsorption fitted well with the Langmuir isotherm model, whereas As(III) data was described perfectly by Freundlich model. The pseudo-second-order kinetic model was fitted well for the entire adsorption process of As(III) and As(V) suggesting that the adsorption is a rate-controlling step. Aqueous solution pH was found to greatly affect the adsorption behavior. Furthermore, co-ions including HCO3(-) and PO4(3-) exhibited greater influence on arsenic removal efficiency, whereas Cl(-), NO3(-), SO4(2-) were found to have negligible effects on arsenic removal. Five consecutive adsorption-regeneration cycles confirmed that the adsorbent could be reusable for successive arsenic treatment and can be used in real treatment applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Performance of Zn-Fe-Mn/MCM-48 sorbents for high temperature H2S removal and analysis of regeneration process

NASA Astrophysics Data System (ADS)

Huang, Z. B.; Liu, B. S.; Wang, F.; Amin, R.

2015-10-01

MCM-48 was synthesized using a rapid and facile process at room temperature. A series of 50%Zn-Fe-Mn/MCM-48 sorbents were prepared and their performance of hot coal gas desulfurization was investigated. High breakthrough sulfur capacity (13.2 g-S/100 g sorbent) and utilization (66.1%) of 50%1Zn2Fe2Mn/MCM-48 sorbent at 550 °C was achieved. The characterization results of XRD, BET, TPR and FT-IR revealed that MCM-48 had excellent thermal stability at less than 700 °C, ZnMn2O4 and (Mn, Zn)Fe2O4 were mainly active particles in fresh sorbents which were highly dispersed on support. The MCM-48 mesoporous structure remained intact after eight successive desulfurization/regeneration cycles. The regeneration process of 50%1Zn2Fe2Mn/MCM-48 sorbent was analyzed, it indicated that the breakthrough sulfur capacity decline of sorbent was due to the migration of Zn onto the sorbent surface and Zn accumulated on the surface and vaporized to the exterior from the surface. In the TPO test, the oxidation of Zn was different for 50%Zn/MCM-48 at 700 °C. It revealed that the temperature of regeneration for ZnO sorbent should be higher than 700 °C.

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

NASA Technical Reports Server (NTRS)

Boclair, J. W.; Braterman, P. S.

1999-01-01

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Specific features of the atomic structure of metallic layers of multilayered (CoFeZr/SiO2)32 and (CoFeZr/ a-Si)40 nanostructures with different interlayers

NASA Astrophysics Data System (ADS)

Domashevskaya, E. P.; Guda, A. A.; Chernyshev, A. V.; Sitnikov, V. G.

2017-02-01

Multilayered nanostructures (MN) were prepared by ion-beam successive sputtering from two targets, one of which was a metallic Co45Fe45Zr10 alloy plate and another target was a quartz (SiO2) or silicon plate on the surface of a rotating glass-ceramic substrate in an argon atmosphere. The Co and Fe K edges X-ray absorption fine structure of XANES in the (CoFeZr/SiO2)32 sample with oxide interlayers was similar to XANES of metallic Fe foil. This indicated the existence in metallic layers of multilayered CoFeZr nanocrystals with a local environment similar to the atomic environment in solid solutions on the base of bcc Fe structure, which is also confirmed by XRD data. XANES near the Co and Fe K edges absorption in another multilayered nanostructure with silicon interlayers (CoFeZr/ a-Si)40 differs from XANES of MN with dielectric SiO2 interlayer, which demonstrates a dominant influence of the Fe-Si and Co-Si bonds in the local environment of 3 d Co and Fe metals when they form CoFeSi-type silicide phases in thinner bilayers of this MN.

Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel

PubMed Central

Gund, Girish S.; Dubal, Deepak P.; Chodankar, Nilesh R.; Cho, Jun Y.; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D.

2015-01-01

The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0–1 V and 0–2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg−1, about 2-fold of higher energy density (41.8 Wh kg−1) than symmetric SC and excellent mechanical flexibility. Furthermore, the “real-life” demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC. PMID:26208144

Low-cost flexible supercapacitors with high-energy density based on nanostructured MnO2 and Fe2O3 thin films directly fabricated onto stainless steel

NASA Astrophysics Data System (ADS)

Gund, Girish S.; Dubal, Deepak P.; Chodankar, Nilesh R.; Cho, Jun Y.; Gomez-Romero, Pedro; Park, Chan; Lokhande, Chandrakant D.

2015-07-01

The facile and economical electrochemical and successive ionic layer adsorption and reaction (SILAR) methods have been employed in order to prepare manganese oxide (MnO2) and iron oxide (Fe2O3) thin films, respectively with the fine optimized nanostructures on highly flexible stainless steel sheet. The symmetric and asymmetric flexible-solid-state supercapacitors (FSS-SCs) of nanostructured (nanosheets for MnO2 and nanoparticles for Fe2O3) electrodes with Na2SO4/Carboxymethyl cellulose (CMC) gel as a separator and electrolyte were assembled. MnO2 as positive and negative electrodes were used to fabricate symmetric SC, while the asymmetric SC was assembled by employing MnO2 as positive and Fe2O3 as negative electrode. Furthermore, the electrochemical features of symmetric and asymmetric SCs are systematically investigated. The results verify that the fabricated symmetric and asymmetric FSS-SCs present excellent reversibility (within the voltage window of 0-1 V and 0-2 V, respectively) and good cycling stability (83 and 91%, respectively for 3000 of CV cycles). Additionally, the asymmetric SC shows maximum specific capacitance of 92 Fg-1, about 2-fold of higher energy density (41.8 Wh kg-1) than symmetric SC and excellent mechanical flexibility. Furthermore, the “real-life” demonstration of fabricated SCs to the panel of SUK confirms that asymmetric SC has 2-fold higher energy density compare to symmetric SC.

Influence of Fe substitution on structural and magnetic features of BiMn2O5 nanostructures

NASA Astrophysics Data System (ADS)

Gaikwad, Vishwajit M.; Goyal, Saveena; Yanda, Premakumar; Sundaresan, A.; Chakraverty, Suvankar; Ganguli, Ashok K.

2018-04-01

Nanostructures of complex oxides [BiFexMn2-xO5 (x = 0, 1, 2)] have been designed to study their structural, optical and magnetic behaviour. X-ray diffraction data (XRD) revealed orthorhombic phase with Pbam space group. Noticeable expansion in unit cell parameters has been found from BiMn2O5 (x = 0) to BiFe2O4.5 (x = 2). The observed structural changes via tuning of B-site (x = 0-2) played an important role in overall magnetic properties. Transmission electron microscopic images confirm that the average particle size of all the materials are in nano domain range with different morphologies. From optical studies, it has been found that the observed energy band gap values are strongly related to 3d electron numbers. These values appear to be larger than that reported for bulk. Isothermal magnetization plots (at 5 K) show increase in coercivity (Hc) from x = 0 to x = 2. Temperature dependent magnetization studies implied anti-ferromagnetic interactions for BiMn2O5, frustrated magnet for BiFeMnO5 and ferromagnetic behaviour for BiFe2O4.5. Ferromagnetic state of nanostructured BiFe2O4.5 is in contrast with its bulk counterparts.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe.

PubMed

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-09-28

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La 3+ -Mn 4+ and Eu 3+ -Fe 3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La 3+ -Mn 4+ and Eu 3+ -Fe 3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications.

Optical and Piezoelectric Study of KNN Solid Solutions Co-Doped with La-Mn and Eu-Fe

PubMed Central

Peña-Jiménez, Jesús-Alejandro; González, Federico; López-Juárez, Rigoberto; Hernández-Alcántara, José-Manuel; Camarillo, Enrique; Murrieta-Sánchez, Héctor; Pardo, Lorena; Villafuerte-Castrejón, María-Elena

2016-01-01

The solid-state method was used to synthesize single phase potassium-sodium niobate (KNN) co-doped with the La3+–Mn4+ and Eu3+–Fe3+ ion pairs. Structural determination of all studied solid solutions was accomplished by XRD and Rietveld refinement method. Electron paramagnetic resonance (EPR) studies were performed to determine the oxidation state of paramagnetic centers. Optical spectroscopy measurements, excitation, emission and decay lifetime were carried out for each solid solution. The present study reveals that doping KNN with La3+–Mn4+ and Eu3+–Fe3+ at concentrations of 0.5 mol % and 1 mol %, respectively, improves the ferroelectric and piezoelectric behavior and induce the generation of optical properties in the material for potential applications. PMID:28773925

Self-Assembly of Metal Oxides into Three-Dimensional Nanostructures: Synthesis and Application in Catalysis

EPA Science Inventory

Nanostructured metal (Fe, Co, Mn, Cr, Mo) oxides were fabricated under microwave irradiation conditions in pure water without using any reducing or capping reagent. The metal oxides self-assembled into octahedron, spheres, triangular rods, pine, and hexagonal snowflake-like thre...

LEAD SORPTION ON RUTHENIUM OXIDE: A MACROSCOPIC AND SPECTROSCOPIC STUDY

EPA Science Inventory

Metal oxide phases play an important role in governing the sorption and desorption mechanisms of metals in water, soils, and sediments. Many researchers have examined the efficiency of Pb sorption on Mn, Fe, Al, Ti, and Si oxide surfaces. Most studies concluded that adsorption ...

Local and average structure of Mn- and La-substituted BiFeO{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Bo; Selbach, Sverre M., E-mail: selbach@ntnu.no

2017-06-15

The local and average structure of solid solutions of the multiferroic perovskite BiFeO{sub 3} is investigated by synchrotron X-ray diffraction (XRD) and electron density functional theory (DFT) calculations. The average experimental structure is determined by Rietveld refinement and the local structure by total scattering data analyzed in real space with the pair distribution function (PDF) method. With equal concentrations of La on the Bi site or Mn on the Fe site, La causes larger structural distortions than Mn. Structural models based on DFT relaxed geometry give an improved fit to experimental PDFs compared to models constrained by the space groupmore » symmetry. Berry phase calculations predict a higher ferroelectric polarization than the experimental literature values, reflecting that structural disorder is not captured in either average structure space group models or DFT calculations with artificial long range order imposed by periodic boundary conditions. Only by including point defects in a supercell, here Bi vacancies, can DFT calculations reproduce the literature results on the structure and ferroelectric polarization of Mn-substituted BiFeO{sub 3}. The combination of local and average structure sensitive experimental methods with DFT calculations is useful for illuminating the structure-property-composition relationships in complex functional oxides with local structural distortions. - Graphical abstract: The experimental and simulated partial pair distribution functions (PDF) for BiFeO{sub 3}, BiFe{sub 0.875}Mn{sub 0.125}O{sub 3}, BiFe{sub 0.75}Mn{sub 0.25}O{sub 3} and Bi{sub 0.9}La{sub 0.1}FeO{sub 3}.« less

Validation of TOF-SIMS and FE-SEM/EDS Techniques Combined with Sorption and Desorption Experiments to Check Competitive and Individual Pb2+ and Cd2+ Association with Components of B Soil Horizons

PubMed Central

Andrade, María Luisa; Vega, Flora A.

2015-01-01

Sorption and desorption experiments were performed by the batch method on the B horizons of five natural soils: Umbric Cambisol, Endoleptic Luvisol, Mollic Umbrisol, Dystric Umbrisol, and Dystric Fluvisol. Individual and competitive sorption and desorption capacity and hysteresis were determined. The results showed that Pb2+ was sorbed and retained in a greater quantity than Cd2+ and that the hysteresis of the first was greater than that of the second. The most influential characteristics of the sorption and retention of Pb2+ were pH, ECEC, Fe and Mn oxides and clay contents. For Cd2+ they were mainly pH and, to a lesser extent, Mn oxides and clay content. The combined use of TOF-SIMS, FE-SEM/EDS and sorption and desorption analyses was suitable for achieving a better understanding of the interaction between soil components and the two heavy metals. They show the preferential association of Pb2+ with vermiculite, chlorite, Fe and Mn oxides, and of Cd2+ with the same components, although to a much lesser extent and intensity. This was due to the latter’s higher mobility as it competed unfavourably with the Pb2+ sorption sites. TOF-SIMS and FE-SEM/EDS techniques confirmed the results of the sorption experiments, and also provided valuable information on whether the soil components (individually or in association) retain Cd2+ and / or Pb2+; this could help to propose effective measures for the remediation of contaminated soils. PMID:25893518

A convenient synthesis of tetrabenzo[de,hi,mn,qr]naphthacene from readily available 1,2-di(phenanthren-4-yl)ethyne.

PubMed

Mukherjee, Anupam; Pati, Kamalkishore; Liu, Rai-Shung

2009-08-21

We report here a convenient synthesis of tetrabenzo[de,hi,mn,qr]naphthacenes from 1,2-di(phenanthren-4-yl)ethynes through initial Brønsted acid-catalyzed hydroarylation, followed by FeCl(3)-oxidative coupling reactions. This new method is applicable to tetrabenzo[de,hi,mn,qr]naphthacenes bearing various alkyl substituents.

Surface Oxidation of the High-Strength Steels Electrodeposited with Cu or Fe and the Resultant Defect Formation in Their Coating during the Following Galvanizing and Galvannealing Processes

NASA Astrophysics Data System (ADS)

Choi, Yun-Il; Beom, Won-Jin; Park, Chan-Jin; Paik, Doojin; Hong, Moon-Hi

2010-12-01

This study examined the surface oxidation of high-strength steels electrodeposited with Cu or Fe and the resultant defect formation in their coating during the following galvanizing and galvannealing processes. The high-strength steels were coated with an Cu or Fe layer by the electroplating method. Then, the coated steels were annealed in a reducing atmosphere, dipped in a molten zinc, and finally transformed into galvannealed steels through the galvannealing process. The formation of Si and Mn oxides on the surface of the high-strength steel was effectively suppressed, and the density of surface defects on the galvanized steel was significantly reduced by the pre-electrodeposition of Cu and Fe. This effect was more prominent for the steels electrodeposited at higher cathodic current densities. The finer electrodeposit layer formed at higher cathodic current density on the steels enabled the suppression of partial surface oxidation by Mn or Si and better wetting of Zn on the surface of the steels in the following galvanizing process. Furthermore, the pre-electrodeposited steels exhibited a smoother surface without surface cracks after the galvannealing process compared with the untreated steel. The diffusion of Fe and Zn in the Zn coating layer in the pre-electrodeposited steels appears to occur more uniformly during the galvannealing process due to the low density of surface defects induced by oxides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan

Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates andmore » aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} exhibit a superparamagnetic behavior.« less

Comparative leaching of six toxic metals from raw and chemically stabilized MSWI fly ash using citric acid.

PubMed

Wang, Huawei; Fan, Xinxiu; Wang, Ya-Nan; Li, Weihua; Sun, Yingjie; Zhan, Meili; Wu, Guizhi

2018-02-15

The leaching behavior of six typical toxic metals (Pb, Zn, Cr, Cd, Cu and Ni) from raw and chemically stabilized (phosphate and chelating agent) municipal solid waste incineration (MSWI) fly ash were investigated using citric acid. Leaching tests indicated that phosphate stabilization can effectively decrease the leaching of Zn, Cd and Cr; whereas chelating agent stabilization shows a strong ability to lower the release of Pb, Cd and Cu, but instead increases the solubility of Zn and Cr at low pH conditions. Sequential extraction results suggested that the leaching of Pb, Zn and Cd in both the stabilized MSWI fly ash samples led to the decrease in Fe/Mn oxide fraction and the increase in exchangeable and carbonate fractions. The leaching of Cr was due to the decrease in exchangeable, carbonate and Fe/Mn oxide fractions in phosphate-stabilized and chelating agent-stabilized MSWI fly ash. The leaching of Cu in both stabilized MSWI fly ash was greatly ascribed to the decrease in Fe/Mn oxide and oxidisable fractions. Moreover, predicted curves by geochemical model indicated that both stabilized MSWI fly ash have the risk of releasing toxic metals under strong acid environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

The influence of redox chemistry and pH on chemically active forms of arsenic in sewage sludge-amended soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carbonell-Barrachina, A.; Jugsujinda, A.; DeLaune, R.D.

1999-07-01

Chemical fractionation procedures were used to quantify the effect of the sediment redox and pH conditions on the adsorption and solubility of arsenic (As) in municipal sewage sludge and sewage sludge-amended soil. Sludge and sludge-amended soil were incubated in microcosms in which Eh-pH conditions were controlled. Samples were sequentially extracted to determine As in various chemical forms (water soluble, exchangeable, bound to carbonates, bound to iron (Fe) and manganese (Mn) oxides, bound to insoluble organics and sulfides) and the chemically inactive fraction (mineral residues). In both sewage sludge and sludge-amended soil, As chemistry was governed by large molecular humic mattermore » and sulfides and Fe and Mn-oxides. Solubility of As remained low and constant under both aerobic and anaerobic conditions in sludge-amended soil. After dissolution of Fe and Mn-oxides, As{sup 5+} was released into sludge solution, reduced to As{sup 3+} and likely precipitated as sulfide. Therefore, an organic amendment rich in sulfur compounds, such as sewage sludge, would drastically reduce the potential risks derived from As pollution under highly anoxic conditions by precipitation of this toxic metalloid as insoluble and immobile sulfides.« less

Structure refinements of members in the brownmillerite solid solution series Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoeber, Stefan, E-mail: stefan.stoeber@geo.uni-halle.de; Redhammer, Guenther; Schorr, Susan

2013-01-15

Four different brownmillerite solid solutions Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3 were synthesized by a solid oxide ceramic method. The phases crystallize either in a primitive centered orthorhombic cell with space group Pnma or in a body centered cell with space group I2mb dependent on the aluminum concentration present in the solid solution. Mn{sup 3+} ions occupy exclusively site 4a coordinated by six oxygen anions. Increasing Mn{sup 3+} concentrations cause a remarkable distortion of the octahedron and indirectly of the tetrahedron, resulting in twisted and tilted octahedral layers as well as buckled tetrahedral chains. The influences aremore » discussed on the site 4a of trivalent manganese due to its Jahn-Teller activity, with regard to the occupation of octahedron and tetrahedron with different sized iron and aluminum ions. - Graphical Abstract: The coupled substitution Fe{sup 3+}>Mn{sup 3+}+Fe{sup 3+} <=>2 Al{sup 3+} in brownmillerite phases (Ca{sub 2}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}Al{sub x}O{sub 5+{delta}}) changes predominantly their structural properties, which is essential for the hydration performance of the calcium aluminate cement, where brownmillerites occur as clinker phases. Highlights: Black-Right-Pointing-Pointer We present structural data of four Ca-Al-Fe-Mn-brownmillerites. Black-Right-Pointing-Pointer Mn{sup 3+}-ions occupy exclusively the octahedrally coordinated site 0,0,0. Black-Right-Pointing-Pointer Bonds and angles of the octahedrally coordinated site are distorted strongly. Black-Right-Pointing-Pointer Mn{sup 3+}-ions influence indirectly the shape of the tetrahedron. Black-Right-Pointing-Pointer Mn{sup 3+}-ions stabilize Pnma instead of I2mb in Ca-Al-Fe-Mn-brownmillerites.« less

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

USGS Publications Warehouse

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Oxidative dissolution potential of biogenic and abiogenic TcO 2 in subsurface sediments

NASA Astrophysics Data System (ADS)

Fredrickson, James K.; Zachara, John M.; Plymale, Andrew E.; Heald, Steve M.; McKinley, James P.; Kennedy, David W.; Liu, Chongxuan; Nachimuthu, Ponnusamy

2009-04-01

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state [Tc(VII)O4-] and less mobile in the reduced form [Tc(IV)O 2· nH 2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO 2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O 2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.

Uptake of elements from seawater by ferromanganese crusts: Solid-phase associations and seawater speciation

USGS Publications Warehouse

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.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

PubMed

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of the domain structure of nano-oxide layers on the transport properties of specular spin valves

NASA Astrophysics Data System (ADS)

Ventura, J.; Sousa, J. B.; Veloso, A.; Freitas, P. P.

2007-05-01

Specular spin valves show enhanced giant magnetoresistive ratio when compared to other simpler, spin valve structures as a result of specular reflection in nano-oxide layers (NOLs) formed by the partial oxidation of the CoFe pinned and free layers. The oxides forming the NOL were recently shown to order antiferromagnetically below T ˜175K. Here we study the training effect in MnIr /CoFe/NOL/CoFe/Cu/CoFe/NOL specular spin valves at low temperatures (15K). We observed that the training effect is related to the nano-oxide layer antiferromagnet ordering and to the evolution of the corresponding domain structure with the number of cycles performed. This allowed us to study the influence of the NOL domain structure on the magnetotransport of specular spin valves.

A new record of silica-rich coating on carbonate substrates in southeast-central Iran: Constraints on geochemical signatures

NASA Astrophysics Data System (ADS)

Aftabi, Alijan; Atapour, Habibeh

2018-10-01

There exist few data on the geochemical signatures and occurrence of silica-rich coatings developed on siliceous carbonate substrates. The rock coatings in the Maran-e-Galu area in southeast-central Iran are composed of four layers; a lower thick layer (1 mm) of silica, a lower thin film of Fe-Mn oxide, an upper thick (1 mm) silica-rich layer, and an upper thin film of Fe-Mn oxide. Energy dispersive X-ray spectrometer (EDS), X-ray diffraction and bulk coating geochemistry data obtained by XRF and ICP-MS highlight that the 1-3 mm thick silica-rich coatings occur as a silica glaze of opal composition on the siliceous carbonate substrate. The coatings were probably formed by the interaction of rainfall, water vapor or dew with silicate and carbonate-rich detrital atmospheric dust, releasing H4SiO4with a pH of 5-10 in this semiarid-arid desert environment. This led to the formation of silica gels as well as minor Fe-Mn oxide gels by evaporation and supersaturation, and finally changed to the black brown silica glaze probably at ambient temperatures of >40 °C Major and minor element signatures are consistent with the known silica glazes, displaying enrichment in Ba, Sr, P, and LREEs with little to no Eu and Ce anomalies and a weak Tm anomaly. However, the very low content of aluminum oxide is well correlated with the known classified silica glaze of genetic type 1, reflecting the absence of detrital clay minerals. The low Fe and Mn contents in bulk coatings (3.6 and 10 magnitudes lower than crustal abundance, respectively) and lack of biochemical processes in the atmospheric dust highlight the semiarid-arid climate setting. We thereby conclude that a new variant of silica glaze of 1-3 mm thickness could form on siliceous carbonate substrates under an alkaline pH in semiarid-arid regions.

Plasma-Sprayed High Entropy Alloys: Microstructure and Properties of AlCoCrFeNi and MnCoCrFeNi

NASA Astrophysics Data System (ADS)

Ang, Andrew Siao Ming; Berndt, Christopher C.; Sesso, Mitchell L.; Anupam, Ameey; S, Praveen; Kottada, Ravi Sankar; Murty, B. S.

2015-02-01

High entropy alloys (HEAs) represent a new class of materials that present novel phase structures and properties. Apart from bulk material consolidation methods such as casting and sintering, HEAs can also be deposited as a surface coating. In this work, thermal sprayed HEA coatings are investigated that may be used as an alternative bond coat material for a thermal barrier coating system. Nanostructured HEAs that were based on AlCoCrFeNi and MnCoCrFeNi were prepared by ball milling and then plasma sprayed. Splat studies were assessed to optimise the appropriate thermal spray parameters and spray deposits were prepared. After mechanical alloying, aluminum-based and manganese-based HEA powders revealed contrary prominences of BCC and FCC phases in their X-ray diffraction patterns. However, FCC phase was observed as the major phase present in both of the plasma-sprayed AlCoCrFeNi and MnCoCrFeNi coatings. There were also minor oxide peaks detected, which can be attributed to the high temperature processing. The measured porosity levels for AlCoCrFeNi and MnCoCrFeNi coatings were 9.5 ± 2.3 and 7.4 ± 1.3 pct, respectively. Three distinct phase contrasts, dark gray, light gray and white, were observed in the SEM images, with the white regions corresponding to retained multicomponent HEAs. The Vickers hardness (HV0.3kgf) was 4.13 ± 0.43 and 4.42 ± 0.60 GPa for AlCoCrFeNi and MnCoCrFeNi, respectively. Both type of HEAs coatings exhibited anisotropic mechanical behavior due to their lamellar, composite-type microstructure.

Siderophore-mediated oxidation of Ce and fractionation of HREE by Mn (hydr)oxide-coprecipitation and sorption on MnO2: Experimental evidence for negative Ce-anomalies in abiogenic manganese precipitates

NASA Astrophysics Data System (ADS)

Krämer, Dennis; Tepe, Nathalie; Bau, Michael

2014-05-01

We conducted experiments with Rare Earths and Yttrium (REY), where the REY were sorbed on synthetic manganese dioxide as well as on coprecipitating manganese (hydr)oxide in the presence and absence of the siderophore desferrioxamine-B (DFOB). Siderophores are a group of globally abundant biogenic complexing agents which are excreted by plants and bacteria to enhance the bioavailability of Fe in oxic environments. The model siderophore used in this study, DFOB, is a hydroxamate siderophore occurring in almost all environmental settings with concentrations in the nanomolar to millimolar range and is one of the most thoroughly studied siderophores. In the absence of siderophores and other organic ligands, trivalent Ce is usually surface-oxidized to tetravalent Ce during sorption onto manganese (hydr)oxides. Such Mn precipitates, therefore, often show positive Ce anomalies, whereas the ambient solutions exhibit negative Ce anomalies (Ohta and Kawabe, 2001). In marked contrast, however, REY sorption in the presence of DFOB produces negative Ce anomalies in the Mn precipitates and a distinct and characteristic positive Ce anomaly in the residual siderophore-bearing solution. Furthermore, the heavy REY with ionic radii larger than the radius of Sm are also almost completely prevented from sorption onto the Mn solid phases. Sorption of REY onto Mn (hydr)oxides in the presence of DFOB creates a distinct and pronounced fractionation of Ce and the heavy REY from the light and middle REY. Apart from Ce, which is oxidized in solution by the siderophore, the distribution of the other REY mimics the stability constants for multi-dentate complexes of REY with DFOB, as determined by Christenson & Schijf (2011). Heavier REY are forming stronger complexes (and are hence better "protected" from sorption) than light REY, excluding Ce. Preferential partitioning of Ce into the liquid phase during the precipitation of Mn (hydr)oxides has only rarely been described for natural Mn (hydr)oxides (e.g., Tanaka et al., 2010, Loges et al., 2012). Our experimental results demonstrate that biogenic organic ligands such as hydroxamate siderophores, may produce solutions with positive Ce anomaly (Bau et al., 2013) and may even counteract the surface oxidation of Ce on Mn (hydr)oxides. References Bau, M., Tepe, N., Mohwinkel, D., 2013. Siderophore-promoted transfer of rare earth elements and iron from volcanic ash into glacial meltwater, river and ocean water. Earth Planet. Sci. Lett. 364, 30-36. Christenson E. A. and Schijf J. (2011) Stability of YREE complexes with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength. Geochim. Cosmochim. Acta 75, 7047-7062. Loges, A., Wagner, T., Barth, M., Bau, M., Göb, S., and Markl, G. 2012. Negative Ce anomalies in Mn oxides: The role of Ce4+ mobility during water-mineral interaction. Geochimica and Cosmochimica Acta 86, 296-317 Ohta A. and Kawabe I. (2001) REE (III) adsorption onto Mn dioxide (delta-MnO2) and Fe oxyhydroxide: Ce(III) oxidation by delta-MnO2. Geochim. Cosmochim. Acta 65, 695-703. Tanaka K., Tani Y., Takahashi Y., Tanimizu M., Suzuki Y., Kozai N. and Ohnuki T. (2010) A specific Ce oxidation process during sorption of rare earth elements on biogenic Mn oxide produced by Acremonium sp. strain KR21-2. Geochim. Cosmochim. Acta 74, 5463-5477.

Effect of nano oxide layer on exchange bias and GMR in Mn-Ir-Pt based spin valve

NASA Astrophysics Data System (ADS)

Jeon, D. M.; Lee, J. P.; Lee, D. H.; Yoon, S. Y.; Kim, Y. S.; Suh, S. J.

2004-05-01

We have investigated the effect of nano oxide layers (NOLs), which were fabricated by a plasma oxidation of CoFe layer on the magnetic properties and magneto-resistance (MR) in a Mn-Ir-Pt based spin valve. The adjusted NOL could result in the high MR and the strong exchange coupling field ( Hex). From a high resolution electron microscopy analysis the oxide was about 1 nm. The strong reflectivity at the interface of a free and oxide capping layer should lead to the decrease of an interlayer coupling field, which could possibly improve the Hex.

Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

PubMed

Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

2015-06-08

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic Evaluation and Optimization of the MnO-B2O3 and MnO-B2O3-SiO2 Systems and Its Application to Oxidation of High-Strength Steels Containing Boron

NASA Astrophysics Data System (ADS)

Kim, Young-Min; Jung, In-Ho

2015-06-01

A complete literature review, critical evaluation, and thermodynamic optimization of phase equilibrium and thermodynamic properties of all available oxide phases in the MnO-B2O3 and MnO-B2O3-SiO2 systems at 1 bar pressure are presented. Due to the lack of the experimental data in these systems, the systematic trend of CaO- and MgO-containing systems were taken into account in the optimization. The molten oxide phase is described by the Modified Quasichemical Model. A set of optimized model parameters of all phases is obtained which reproduces all available and reliable thermodynamic and phase equilibrium data. The unexplored binary and ternary phase diagrams of the MnO-B2O3 and MnO-B2O3-SiO2 systems have been predicted for the first time. The thermodynamic calculations relevant to the oxidation of advanced high-strength steels containing boron were performed to find that B can form liquid B2O3-SiO2-rich phase in the annealing furnace under reducing N2-H2 atmosphere, which can significantly influence the wetting behavior of liquid Zn in Zn galvanizing process.

SODa: an Mn/Fe superoxide dismutase prediction and design server.

PubMed

Kwasigroch, Jean Marc; Wintjens, René; Gilis, Dimitri; Rooman, Marianne

2008-06-02

Superoxide dismutases (SODs) are ubiquitous metalloenzymes that play an important role in the defense of aerobic organisms against oxidative stress, by converting reactive oxygen species into nontoxic molecules. We focus here on the SOD family that uses Fe or Mn as cofactor. The SODa webtool http://babylone.ulb.ac.be/soda predicts if a target sequence corresponds to an Fe/Mn SOD. If so, it predicts the metal ion specificity (Fe, Mn or cambialistic) and the oligomerization mode (dimer or tetramer) of the target. In addition, SODa proposes a list of residue substitutions likely to improve the predicted preferences for the metal cofactor and oligomerization mode. The method is based on residue fingerprints, consisting of residues conserved in SOD sequences or typical of SOD subgroups, and of interaction fingerprints, containing residue pairs that are in contact in SOD structures. SODa is shown to outperform and to be more discriminative than traditional techniques based on pairwise sequence alignments. Moreover, the fact that it proposes selected mutations makes it a valuable tool for rational protein design.

Mechanisms of Arsenic Mobilization and Attenuation in Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Root, R.; Choi, S.; Vlassopoulos, D.

2007-12-01

This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited in labile or available S and/or Fe that remove As by precipitation or adsorption. In subsurface sediments with low labile S and Fe, laboratory experiments and spectroscopic studies suggest that sediment Mn minerals are important in the oxidation of sorbed As(III) to As(V), but that they have a limited oxidation capacity. Arsenic attenuation and mobilization in the subsurface are affected by seasonal variations when hydraulic conditions are influenced by surface infiltration, which may induce transitions from oxidized to reduced conditions (or vice versa) in porewater.

A Holistic Model That Physicochemically Links Iron Oxide - Apatite and Iron Oxide - Copper - Gold Deposits to Magmas

NASA Astrophysics Data System (ADS)

Simon, A. C.; Reich, M.; Knipping, J.; Bilenker, L.; Barra, F.; Deditius, A.; Lundstrom, C.; Bindeman, I. N.

2015-12-01

Iron oxide-apatite (IOA) and iron oxide-copper-gold deposits (IOCG) are important sources of their namesake metals and increasingly for rare earth metals in apatite. Studies of natural systems document that IOA and IOCG deposits are often spatially and temporally related with one another and coeval magmatism. However, a genetic model that accounts for observations of natural systems remains elusive, with few observational data able to distinguish among working hypotheses that invoke meteoric fluid, magmatic-hydrothermal fluid, and immiscible melts. Here, we use Fe and O isotope data and high-resolution trace element (e.g., Ti, V, Mn, Al) data of individual magnetite grains from the world-class Los Colorados (LC) IOA deposit in the Chilean Iron Belt to elucidate the origin of IOA and IOCG deposits. Values of d56Fe range from 0.08‰ to 0.26‰, which are within the global range of ~0.06‰ to 0.5‰ for magnetite formed at magmatic conditions. Values of δ18O for magnetite and actinolite are 2.04‰ and 6.08‰, respectively, consistent with magmatic values. Ti, V, Al, and Mn are enriched in magnetite cores and decrease systematically from core to rim. Plotting [Al + Mn] vs. [Ti + V] indicates that magnetite cores are consistent with magmatic and/or magmatic-hydrothermal (i.e., porphyry) magnetites. Decreasing Al, Mn, Ti, V is consistent with a cooling trend from porphyry to Kiruna to IOCG systems. The data from LC are consistent with the following new genetic model for IOA and IOCG systems: 1) magnetite cores crystallize from silicate melt; 2) these magnetite crystals are nucleation sites for aqueous fluid that exsolves and scavenges inter alia Fe, P, S, Cu, Au from silicate melt; 3) the magnetite-fluid suspension is less dense that the surrounding magma, allowing ascent; 4) as the suspension ascends, magnetite grows in equilibrium with the fluid and takes on a magmatic-hydrothermal character (i.e., lower Al, Mn, Ti, V); 5) during ascent, magnetite, apatite and actinolite are deposited to form IOA deposits; 6) the further ascending fluid transports Fe, Cu, Au and S toward the surface where metal-oxides and metal-sulfides precipitate to form IOCG deposits. This model is globally applicable and explains the observed temporal and spatial relationship between magmatism and formation of IOA and IOCG deposits.

Fe-Ti oxide geothermometry: thermodynamic formulation and the estimation of intensive variables in silicic magmas

NASA Astrophysics Data System (ADS)

Ghiorso, Mark S.; Sack, O.

1991-10-01

A new thermodynamic formulation of the Fe-Ti oxide geothermometer/oxygen barometer is developed. The method is based upon recently calibrated models for spinel solid solutions in the quinary system (Fe2+, Mg)(Al,Fe3+,Cr)2O4-(Fe2+, Mg)2TiO4 by Sack and Ghiorso, and rhombohedral oxides in the quaternary system (Fe2+,Mg,Mn)TiO3-Fe2O3 (this paper). The formulation is internally consistent with thermodynamic models for (Fe2+,Mg)-olivine and -orthopyroxene solid solutions and end-member thermodynamic properties tabulated by Berman. The constituent expressions account for compositional and temperature dependent cation ordering and reproduce miscibility gap features in all of the component binaries. The calibration does not account for the excess Gibbs energy resulting from compositional and temperature dependent magnetic ordering in either phase. This limits application of the method to assemblages that equilibrated at temperatures above 600° C. Practical implementation of the proposed geothermometer/oxygen barometer requires minimal use of projection algorthms in accommodating compositions of naturally occurring phases. The new formulation is applied to the estimation of temperature and oxygen fugacity in a wide variety of intermediate to silicic volcanic rocks. In combination with previous work on olivine and orthopyroxene thermodynamics, equilibration pressures are computed for a subset of these volcanics that contain the assemblage quartz, oxides and either ferromagnesian silicate. The calculated log10 f O 2- T relations are reflected in coexisting ferromagnesian mineral assemblages. Volcanics with the lowest relative oxygen fugacity (Δlog10 f O 2) are characterized by the assemblage olivine-quartz, those with slightly higher Δ log10 f O 2 s, by the assemblage orthopyroxene-quartz. The sequence proceeds with the necessary phases biotite-feldspar, then hornblende-quartz-clinopyroxene, and finally at the highest Δ log10 f O 2 s, sphene-quartz-clinopyroxene. Quantitative analysis of these trends, utilizing thermodynamic data for the constituent phases, establishes that, in most cases, the T-log10 f O 2value computed from the oxides is consistent with the compositions of coexisting silicate phases, indicating that phenocryst equilibrium was achieved prior to eruption. There is, however, considerable evidence of oxide-silicate disequilibrium in samples collected from more slowly cooled domes and obsidians. In addition, T-log10 f O 2trends from volcanic rocks that contain biotite and orthopyroxene are interpreted to imply a condition of Fe2+-Mg exchange disequilibrium between orthopyroxene and coexisting ferromagnesian silicates and melt. It is suspected that many biotite-feldspar-quartz-orthopyroxene bearing low temperature volcanic rocks inherit orthopyroxene xenocrysts which crystallized earlier in the cooling history of the magma body.

Possible roles of manganese redox chemistry in the sulfur cycle

NASA Technical Reports Server (NTRS)

Nealson, K. H.

1985-01-01

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Dimensionally stable metallic hydride composition

DOEpatents

Heung, Leung K.

1994-01-01

A stable, metallic hydride composition and a process for making such a composition. The composition comprises a uniformly blended mixture of a metal hydride, kieselguhr, and a ballast metal, all in the form of particles. The composition is made by subjecting a metal hydride to one or more hydrogen absorption/desorption cycles to disintegrate the hydride particles to less than approximately 100 microns in size. The particles are partly oxidized, then blended with the ballast metal and the kieselguhr to form a uniform mixture. The mixture is compressed into pellets and calcined. Preferably, the mixture includes approximately 10 vol. % or more kieselguhr and approximately 50 vol. % or more ballast. Metal hydrides that can be used in the composition include Zr, Ti, V, Nb, Pd, as well as binary, tertiary, and more complex alloys of La, Al, Cu, Ti, Co, Ni, Fe, Zr, Mg, Ca, Mn, and mixtures and other combinations thereof. Ballast metals include Al, Cu and Ni.

ROLE OF MANGANESE REDUCTION/OXIDATION (REDOX) ON FOAMING AND MELT RATE IN HIGH LEVEL WASTE (HLW) MELTERS (U)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jantzen, C; Michael Stone, M

2007-03-30

High-level nuclear waste is being immobilized at the Savannah River Site (SRS) by vitrification into borosilicate glass at the Defense Waste Processing Facility (DWPF). Control of the Reduction/Oxidation (REDOX) equilibrium in the DWPF melter is critical for processing high level liquid wastes. Foaming, cold cap roll-overs, and off-gas surges all have an impact on pouring and melt rate during processing of high-level waste (HLW) glass. All of these phenomena can impact waste throughput and attainment in Joule heated melters such as the DWPF. These phenomena are caused by gas-glass disequilibrium when components in the melter feeds convert to glass andmore » liberate gases such as H{sub 2}O vapor (steam), CO{sub 2}, O{sub 2}, H{sub 2}, NO{sub x}, and/or N{sub 2}. During the feed-to-glass conversion in the DWPF melter, multiple types of reactions occur in the cold cap and in the melt pool that release gaseous products. The various gaseous products can cause foaming at the melt pool surface. Foaming should be avoided as much as possible because an insulative layer of foam on the melt surface retards heat transfer to the cold cap and results in low melt rates. Uncontrolled foaming can also result in a blockage of critical melter or melter off-gas components. Foaming can also increase the potential for melter pressure surges, which would then make it difficult to maintain a constant pressure differential between the DWPF melter and the pour spout. Pressure surges can cause erratic pour streams and possible pluggage of the bellows as well. For these reasons, the DWPF uses a REDOX strategy and controls the melt REDOX between 0.09 {le} Fe{sup 2+}/{summation}Fe {le} 0.33. Controlling the DWPF melter at an equilibrium of Fe{sup +2}/{summation}Fe {le} 0.33 prevents metallic and sulfide rich species from forming nodules that can accumulate on the floor of the melter. Control of foaming, due to deoxygenation of manganic species, is achieved by converting oxidized MnO{sub 2} or Mn{sub 2}O{sub 3} species to MnO during melter preprocessing. At the lower redox limit of Fe{sup +2}/{summation}Fe {approx} 0.09 about 99% of the Mn{sup +4}/Mn{sup +3} is converted to Mn{sup +2}. Therefore, the lower REDOX limits eliminates melter foaming from deoxygenation.« less

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE PAGES

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing; ...

2017-07-05

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Investigation of the Effect of Alloying Elements and Water Vapor Contents on the Oxidation and Decarburization of Transformation-Induced Plasticity Steels

NASA Astrophysics Data System (ADS)

Zhang, Z. T.; Sohn, I. R.; Pettit, F. S.; Meier, G. H.; Sridhar, S.

2009-08-01

The present research deals with an investigation of the effect of alloying element additions (Si, P, and Sb) and water vapor content ({{{{{P}}_{{{{H}}_{ 2} {{O}}}} } {{{P}}_{{{{H}}_{ 2} }} }}} = 0.01{{ to }}0.13}) on the oxidation and decarburization behavior of transformation-induced plasticity (TRIP) steels in a gas mixture of 95 vol pct argon and 5 vol pct hydrogen/steam, by thermogravimetry (TG). The oxidation proceeds primarily as an internal oxidation front in the TRIP steels, but a thin external scale on the order of a micrometer thickness exists and is comprised primarily of fayalite ((Mn,Fe)2SiO4) and ((MnO) x (FeO)1- x . The oxidation products are distributed near the surface and along grain boundaries. A comparison between calculated and measured oxidation curves indicated that the oxidation and decarburization are independent. The results for TRIP steels, both with and without an Sb addition, indicate that increasing Si and P contents accelerate, whereas Sb addition suppresses, both decarburization and oxidation rates. Water vapor content has no obvious effect on decarburization but has a pronounced effect on oxidation, and decreasing water vapor content decreases the oxidation rates.

Ferroelectric control of a Mott insulator

PubMed Central

Yamada, Hiroyuki; Marinova, Maya; Altuntas, Philippe; Crassous, Arnaud; Bégon-Lours, Laura; Fusil, Stéphane; Jacquet, Eric; Garcia, Vincent; Bouzehouane, Karim; Gloter, Alexandre; Villegas, Javier E.; Barthélémy, Agnès; Bibes, Manuel

2013-01-01

The electric field control of functional properties is an important goal in oxide-based electronics. To endow devices with memory, ferroelectric gating is interesting, but usually weak compared to volatile electrolyte gating. Here, we report a very large ferroelectric field-effect in perovskite heterostructures combining the Mott insulator CaMnO3 and the ferroelectric BiFeO3 in its “supertetragonal” phase. Upon polarization reversal of the BiFeO3 gate, the CaMnO3 channel resistance shows a fourfold variation around room temperature, and a tenfold change at ~200 K. This is accompanied by a carrier density modulation exceeding one order of magnitude. We have analyzed the results for various CaMnO3 thicknesses and explain them by the electrostatic doping of the CaMnO3 layer and the presence of a fixed dipole at the CaMnO3/BiFeO3 interface. Our results suggest the relevance of ferroelectric gates to control orbital- or spin-ordered phases, ubiquitous in Mott systems, and pave the way toward efficient Mott-tronics devices. PMID:24089020

Evidence for biogenic processes during formation of ferromanganese crusts from the Pacific Ocean: implications of biologically induced mineralization.

PubMed

Wang, Xiao-Hong; Schlossmacher, Ute; Natalio, Filipe; Schröder, Heinz C; Wolf, Stephan E; Tremel, Wolfgang; Müller, Werner E G

2009-01-01

Ferromanganese [Fe/Mn] crusts formed on basaltic seamounts, gain considerable economic importance due to their high content of Co, Ni, Cu, Zn and Pt. The deposits are predominantly found in the Pacific Ocean in depths of over 1000m. They are formed in the mixing layer between the upper oxygen-minimum zone and the lower oxygen-rich bottom zone. At present an almost exclusive abiogenic origin of crust formation is considered. We present evidence that the upper layers of the crusts from the Magellan Seamount cluster are very rich in coccoliths/coccolithophores (calcareous phytoplankton) belonging to different taxa. Rarely intact skeletons of these unicellular algae are found, while most of them are disintegrated into their composing prisms or crystals. Studies on the chemical composition of crust samples by high resolution SEM combined with an electron probe microanalyzer (EPMA) revealed that they are built of distinct stacked piles of individual compartments. In the center of such piles Mn is the dominant element, while the rims of the piles are rich in Fe (mineralization aspect). The compartments contain coccospheres usually at the basal part. Energy dispersive X-ray spectroscopy (EDX) analyses showed that those coccospheres contain, as expected, CaCO3 but also Mn-oxide. Detailed analysis displayed on the surface of the coccolithophores a high level of CaCO3 while the concentration of Mn-oxide is relatively small. With increasing distance from the coccolithophores the concentration of Mn-oxide increases on the expense of residual CaCO3. We conclude that coccoliths/coccolithophores are crucial for the seed/nucleation phase of crust formation (biomineralization aspect). Subsequently, after the biologically induced mineralization phase Mn-oxide deposition proceeds "auto"catalytically.

Effects of alternative electron acceptors on the activity and community structure of methane-producing and consuming microbes in the sediments of two shallow boreal lakes.

PubMed

Rissanen, Antti J; Karvinen, Anu; Nykänen, Hannu; Peura, Sari; Tiirola, Marja; Mäki, Anita; Kankaala, Paula

2017-07-01

The role of anaerobic CH4 oxidation in controlling lake sediment CH4 emissions remains unclear. Therefore, we tested how relevant EAs (SO42-, NO3-, Fe3+, Mn4+, O2) affect CH4 production and oxidation in the sediments of two shallow boreal lakes. The changes induced to microbial communities by the addition of Fe3+ and Mn4+ were studied using next-generation sequencing targeting the 16S rRNA and methyl-coenzyme M reductase (mcrA) genes and mcrA transcripts. Putative anaerobic CH4-oxidizing archaea (ANME-2D) and bacteria (NC 10) were scarce (up to 3.4% and 0.5% of archaeal and bacterial 16S rRNA genes, respectively), likely due to the low environmental stability associated with shallow depths. Consequently, the potential anaerobic CH4 oxidation (0-2.1 nmol g-1dry weight (DW)d-1) was not enhanced by the addition of EAs, nor important in consuming the produced CH4 (0.6-82.5 nmol g-1DWd-1). Instead, the increased EA availability suppressed CH4 production via the outcompetition of methanogens by anaerobically respiring bacteria and via the increased protection of organic matter from microbial degradation induced by Fe3+ and Mn4+. Future studies could particularly assess whether anaerobic CH4 oxidation has any ecological relevance in reducing CH4 emissions from the numerous CH4-emitting shallow lakes in boreal and tundra landscapes. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Effect of Fe-Mn addition on microstructure and magnetic properties of NdFeB magnetic powders

NASA Astrophysics Data System (ADS)

Kurniawan, C.; Purba, A. S.; Setiadi, E. A.; Simbolon, S.; Warman, A.; Sebayang, P.

2018-03-01

In this paper, the effect of Fe-Mn alloy addition on microstructures and magnetic properties of NdFeB magnetic powders was investigated. Varied Fe-Mn compositions of 1, 5, and 10 wt% were mixed with commercial NdFeB type MQA powders for 15 minutes using shaker mill. The characterizations were performed by powder density, PSA, XRD, SEM, and VSM. The Fe-Mn addition increased the powder density of NdFeB/Fe-Mn powders. On the other side, particle size distribution slightly decreased as the Fe-Mn composition increases. Magnetic properties of NdFeB/Fe-Mn powders changed with the increasing of Fe-Mn content. SEM analysis showed the particle size of NdFeB/Fe-Mn powder was smaller as the Fe-Mn composition increases. It showed that NdFeB/Fe-Mn particles have different size and shape for NdFeB and Fe-Mn particles separately. The optimum magnetic properties of NdFeB/Fe-Mn powder was achieved on the 5 wt% Fe-Mn composition with remanence M r = 49.45 emu/g, coercivity H c = 2.201 kOe, and energy product, BH max = 2.15 MGOe.

Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Takahashi, Yoshio; Marcus, Matthew A.; Uruga, Tomoya; Tanida, Hajime; Terada, Yasuko; Usui, Akira

2013-04-01

The tungsten (W) species in marine ferromanganese oxides were investigated by wavelength dispersive XAFS method. We found that the W species are in distorted Oh symmetry in natural ferromanganese oxides. The host phase of W is suggested to be Mn oxides by μ-XRF mapping. We also found that the W species forms inner-sphere complexes in hexavalent state and distorted Oh symmetry on synthetic ferrihydrite, goethite, hematite, and δ-MnO2. The molecular-scale information of W indicates that the negatively-charged WO42- ion mainly adsorbs on the negatively-charged Mn oxides phase in natural ferromanganese oxides due to the strong chemical interaction. In addition, preferential adsorption of lighter W isotopes is expected based on the molecular symmetry of the adsorbed species, implying the potential significance of the W isotope systems similar to Mo. Adsorption experiments of W on synthetic ferrihydrite and δ-MnO2 were also conducted. At higher equilibrium concentration, W exhibits behaviors similar to Mo on δ-MnO2 due to their formations of inner-sphere complexes. On the other hand, W shows a much larger adsorption on ferrihydrite than Mo. This is due to the formation of the inner- and outer-sphere complexes for W and Mo on ferrihydrite, respectively. Considering the lower equilibrium concentration such as in oxic seawater, however, the enrichment of W into natural ferromanganese oxides larger than Mo may be controlled by the different stabilities of their inner-sphere complexes on the Mn oxides. These two factors, (i) the stability of inner-sphere complexes on the Mn oxides and (ii) the mode of attachment on ferrihydrite (inner- or outer-sphere complex), are the causes of the different behaviors of W and Mo on the surface of the Fe/Mn (oxyhydr)oxides.

Catalytic ozonation of aqueous phenol over metal-loaded HZSM-5.

PubMed

Amin, Nor Aishah Saidina; Akhtar, Javaid; Rai, H K

2011-01-01

The performances of HZSM-5 and transition metal-loaded HZSM-5 (Mn, Cu, Fe, Ti) catalysts during catalytic ozonation of phenol have been investigated. It was observed the performance order for removal of phenol and COD was Mn/HZSM-5 > Fe/HZSM-5 > Cu/HZSM-5 > Ti/HZSM-5 > HZSM-5. The presence of metals on HZSM-5 enhanced the phenol removal capability of HZSM-5. Mn loading on HZSM-5 was optimized due to its high phenol removal capability amongst metal-loaded HZSM-5 catalysts. Experimental results suggested that low amount of Mn loading on HZSM-5 was sufficient for HZSM-5 to act as catalyst and adsorbent. A maximum of 95.8 wt% phenols and 70.2 wt% COD were removed over 2 wt% Mn/HZSM-5 in 120 min. It was supposed that transition metals mainly acted as ozone decomposers due to their multiple oxidation states that enhanced the ozonation of phenol.

Distinct effects of Al3+ doping on the structure and properties of hexagonal turbostratic birnessite: A comparison with Fe3+ doping

NASA Astrophysics Data System (ADS)

Yin, Hui; Kwon, Kideok D.; Lee, Jin-Yong; Shen, Yi; Zhao, Huaiyan; Wang, Xiaoming; Liu, Fan; Zhang, Jing; Feng, Xionghan

2017-07-01

Hexagonal turbostratic birnessite, one of the most reactive Mn oxide minerals, is ubiquitous throughout the ocean floor to the surface environment. During its crystallization, birnessite may coexist with Al3+, which is the third most abundant crustal element. However, interactions of Al3+ with birnessite compared to the transition metal (TM) ions have rarely been explored thus far. This study examines the structure and properties of Al3+-doped hexagonal turbostratic birnessite to obtain insights into the interaction of metal cations with birnessite-like minerals in natural environments. For Al3+-incorporated birnessite, the crystal chemistry of Al3+, as well as alteration in the mineral structure, physicochemical properties, and reactivity toward the sorption of Pb2+/Zn2+ is investigated by powder X-ray diffraction, chemical analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Electronic structure calculations based on density functional theory (DFT) are further combined to aid in the experimental interpretation of Al3+ incorporation. As a comparative system, Fe3+-coprecipitated birnessite is also examined. Under the experimental conditions used, only a small amount of Al3+ is incorporated into birnessite, with a final Al/(Al + Mn) molar ratio of ∼0.07, whereas Fe3+ is incorporated into birnessite with a final Fe/(Fe + Mn) molar ratio of up to ∼0.21. Irrespective of metal type, the incorporation of a metal cation significantly alters the physicochemical properties of birnessite, such as decrease in the thickness of crystals along the c∗ axis and coherent scattering domain sizes in the a-b plane and the Mn average oxidation state, increase in the specific surface area and the total amount of hydroxyl groups, in which the contents of hydroxyl groups around vacancies are decreased. The lattice parameters in the a-b plane tend to decrease in Al-incorporated birnessites but first significantly decrease and then increase in Fe-incorporated birnessites. In Fe-incorporated birnessites, ∼32-50% of the total Fe3+ is located inside the Mn octahedral sheets (INC species). In Al-incorporated birnessites, the edge- and corner-sharing Mn-Mn distances gradually decrease. Density function theory (DFT) computation results support that the dominant species in Al-birnessite is a triple-corner-sharing complex on vacancies. The DFT geometry optimization further demonstrates that the in-plane cell size experimentally observed for these birnessites depends on not only the metal type but also its position in the mineral. The Al- or Fe-birnessites exhibit significantly increased adsorption capacities for Pb2+ but reduced capacities for Zn2+. The metal incorporation effects on the chemical reactivity are discussed with the observed changes in the particle size and available vacancy sites.

[The role of oxidative metabolism disturbance in the development of NO-related endothelial dysfunction during chronic hearth failure].

PubMed

Goishvili, N; Kakauridze, N; Sanikidze, T

2005-05-01

The aim of the work was to establish the oxidative metabolism changes and NO data in Chronic Hearth Failure (HF). 52 patients were included in the investigation, among them 37 patients with CHD and chronic HF (II-IV functional class by NIHA) and 17 without it (control group). For revealing of organism redox-status (ceruloplasmine, Fe3+-transfferine, Mn2+, methemoglobine) the blood paramagnetic centers was studied by electron paramagnetic resonance method. For revealing of blood free NO, the diethyldithiocarbamat (SIGMA) was used. In chronic HF the oxidative process intensification and organism compensate reaction reduction with low Fe3+-transferine levels, increased Mn2++, methaemoglobin and inactivation of erythrocytes membranes adrenergic receptors were revealed. In chronic HF the accumulation of reactive oxygen levels provoke NO transformation in peroxynitrote with following decreases of blood free NO and develop the endothelial dysfunction.

Effect of La0.1Sr0.9Co0.5Mn0.5O3-δ protective coating layer on the performance of La0.6Sr0.4Co0.8Fe0.2O3-δ solid oxide fuel cell cathode

NASA Astrophysics Data System (ADS)

Chou, Ping-Yi; Ciou, Chun-Jing; Lee, Yu-Chen; Hung, I.-Ming

2012-01-01

This study investigates the interface reactivity between La0.1Sr0.9Co0.5Mn0.5O3-δ (LSCM) protective coating layer and Crofer22H interconnects. Additionally, we report the mechanism of Cr poisoning of the La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) cathode's electrochemical properties. The phase, chemical composition, and element distribution of compounds formed at the LSCM-Crofer22H interface are analyzed by X-ray diffraction (XRD) and electron dispersive microscopy (EDS). After heat treatment at 800 °C for 100 h, the LSCM/Crofer22H sample contains SrCrO3, a compound with good conductivity; the area specific resistance (ASR) for the LSCM/Crofer22H interconnect is approximately 17-40 mΩ cm2. We found that the amount of (Mn0.98Fe0.02)(Mn0.02Fe0.48Cr1.5)O4, Cr3O4, and (Fe,Cr)2O3 oxides form in LSCF/LSCM/Crofer22H is significantly less than that in LSCF/Crofer22H. LSCF conductivity after heating at 800 °C for 100 h, is notably higher when in contact with LSCM/Crofer22H than it is when in contact with Crofer22H. These results demonstrate that the LSCM protective coating prevents LSCF cathode poisoning by Cr evaporated from the Corfer22H interconnects.

Application of sequential leaching, risk indices and multivariate statistics to evaluate heavy metal contamination of estuarine sediments: Dhamara Estuary, East Coast of India.

PubMed

Asa, Subas Chandra; Rath, Prasanta; Panda, Unmesh Chandra; Parhi, Pankaj Kumar; Bramha, Satyanarayan

2013-08-01

In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe-Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe-Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.

Electrical conduction mechanism of LaNi{sub x}Me{sub 1−x}O{sub 3−δ} (Me = Fe, Mn)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niwa, Eiki, E-mail: e-niwa@phys.chs.nihon-u.ac.jp; Department of Integrated Sciences in Physics and Biology, College of Humanities and Sciences, Nihon University, Setagaya-ku, Tokyo 156-8550; Maeda, Hiroki

Graphical abstract: Compositional dependence of (a) electrical conductivity and (b) E{sub a} for hopping conduction of LaNi{sub x}Me{sub 1−x}O{sub 3} (Me = Fe, Mn). - Highlights: • Electrical conduction mechanism of LaNi{sub x}Me{sub 1−x}O{sub 3} (Me = Fe, Mn) was investigated. • Hopping conduction model could be applied for conductivity of both specimens. • The difference of E{sub a} due to that of energy level of Fe and Mn was observed. • Hole concentration estimated by iodimetry increases with increasing Ni content. - Abstract: Electrical conduction mechanism of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} expected as Sr-freemore » new cathode material for solid oxide fuel cells was analyzed. Electrical conduction behaviors of both specimens could be well fitted by small polaron hopping conduction model. The electrical conductivity of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} increased with increasing Ni content, showing agreement with decrease of activation energy for hopping conduction. The decrease of electrical conductivity and increase of activation energy of LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} were observed with increasing Ni content for 0.0 ≤ x ≤ 0.4. Further Ni substitution increased electrical conductivity and decreased activation energy for 0.4 ≤ x ≤ 0.6. It was revealed using iodometry that the difference of hole carrier density between LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1−x}O{sub 3+δ} was small. It was suspected that the origin of the difference of electrical conduction behavior of LaNi{sub x}Fe{sub 1−x}O{sub 3−δ} and LaNi{sub x}Mn{sub 1-x}O{sub 3+δ} was difference of energy level of e{sub g} band composed of Fe 3d or Mn 3d orbitals and their overlapping quantity with O 2p and Ni 3d band.« less

Chemical fractionation of heavy metals in urban soils of Guangzhou, China.

PubMed

Lu, Ying; Zhu, Feng; Chen, Jie; Gan, Haihua; Guo, Yanbiao

2007-11-01

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominantly located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron-Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.

Metal ferrite oxygen carriers for chemical looping combustion of solid fuels

DOEpatents

Siriwardane, Ranjani V.; Fan, Yueying

2017-01-31

The disclosure provides a metal ferrite oxygen carrier for the chemical looping combustion of solid carbonaceous fuels, such as coal, coke, coal and biomass char, and the like. The metal ferrite oxygen carrier comprises MFe.sub.xO.sub.y on an inert support, where MFe.sub.xO.sub.y is a chemical composition and M is one of Mg, Ca, Sr, Ba, Co, Mn, and combinations thereof. For example, MFe.sub.xO.sub.y may be one of MgFe.sub.2O.sub.4, CaFe.sub.2O.sub.4, SrFe.sub.2O.sub.4, BaFe.sub.2O.sub.4, CoFe.sub.2O.sub.4, MnFeO.sub.3, and combinations thereof. The MFe.sub.xO.sub.y is supported on an inert support. The inert support disperses the MFe.sub.xO.sub.y oxides to avoid agglomeration and improve performance stability. In an embodiment, the inert support comprises from about 5 wt. % to about 60 wt. % of the metal ferrite oxygen carrier and the MFe.sub.xO.sub.y comprises at least 30 wt. % of the metal ferrite oxygen carrier. The metal ferrite oxygen carriers disclosed display improved reduction rates over Fe.sub.2O.sub.3, and improved oxidation rates over CuO.

Identification of ground-state spin ordering in antiferromagnetic transition metal oxides using the Ising model and a genetic algorithm

PubMed Central

Lee, Kyuhyun; Youn, Yong; Han, Seungwu

2017-01-01

Abstract We identify ground-state collinear spin ordering in various antiferromagnetic transition metal oxides by constructing the Ising model from first-principles results and applying a genetic algorithm to find its minimum energy state. The present method can correctly reproduce the ground state of well-known antiferromagnetic oxides such as NiO, Fe2O3, Cr2O3 and MnO2. Furthermore, we identify the ground-state spin ordering in more complicated materials such as Mn3O4 and CoCr2O4. PMID:28458746

In situ arsenic removal in an alkaline clastic aquifer

USGS Publications Warehouse

Welch, A.H.; Stollenwerk, K.G.; Paul, A.P.; Maurer, D.K.; Halford, K.J.

2008-01-01

In situ removal of As from ground water used for water supply has been accomplished elsewhere in circum-neutral ground water containing high dissolved Fe(II) concentrations. The objective of this study was to evaluate in situ As ground-water treatment approaches in alkaline ground-water (pH > 8) that contains low dissolved Fe (

Water-Soluble Fe(II)−H2O Complex with a Weak O−H Bond Transfers a Hydrogen Atom via an Observable Monomeric Fe(III)−OH

PubMed Central

Brines, Lisa M.; Coggins, Michael K.; Poon, Penny Chaau Yan; Toledo, Santiago; Kaminsky, Werner; Kirk, Martin L.

2015-01-01

Understanding the metal ion properties that favor O−H bond formation versus cleavage should facilitate the development of catalysts tailored to promote a specific reaction, e.g., C−H activation or H2O oxidation. The first step in H2O oxidation involves the endothermic cleavage of a strong O−H bond (BDFE = 122.7 kcal/mol), promoted by binding the H2O to a metal ion, and by coupling electron transfer to proton transfer (PCET). This study focuses on details regarding how a metal ion’s electronic structure and ligand environment can tune the energetics of M(HO−H) bond cleavage. The synthesis and characterization of an Fe(II)−H2O complex, 1, that undergoes PCET in H2O to afford a rare example of a monomeric Fe(III)−OH, 7, is described. High-spin 7 is also reproducibly generated via the addition of H2O to {[FeIII(OMe2N4(tren))]2-(µ-O)}2+ (8). The O−H bond BDFE of Fe(II)−H2O (1) (68.6 kcal/mol) is calculated using linear fits to its Pourbaix diagram and shown to be 54.1 kcal/mol less than that of H2O and 10.9 kcal/mol less than that of [Fe(II)(H2O)6]2+. The O−H bond of 1 is noticeably weaker than the majority of reported Mn+(HxO−H) (M = Mn, Fe; n+ = 2+, 3+; x = 0, 1) complexes. Consistent with their relative BDFEs, Fe(II)−H2O (1) is found to donate a H atom to TEMPO•, whereas the majority of previously reported Mn+−O(H) complexes, including [MnIII(SMe2N4(tren))(OH)]+ (2), have been shown to abstract H atoms from TEMPOH. Factors responsible for the weaker O−H bond of 1, such as differences in the electron-donating properties of the ligand, metal ion Lewis acidity, and electronic structure, are discussed. PMID:25611075

Ionic configuration of copper ferrimanganites Cu 0.5Mn xFe 2.5- xO 4

NASA Astrophysics Data System (ADS)

Lenglet, M.; Kasperek, J.; Hannoyer, B.; Lopitaux, J.; d'Huysser, A.; Tellier, J. C.

1992-06-01

Mössbauer spectrometry, neutron diffraction, XANES, and XPS have led to the determination of the cation distributions of the system Cu 0.5Mn xFe 2.5- xO 4 (0≤ x≤1.5). The three cations are present in both tetrahedral and octahedral sites, and the relative number of Fe ions on A- and B-sites remains nearly constant in the whole range of x. It appears that for x≤0.5 manganese is divalent and copper is in its two oxidation states. For x>0.5 copper and iron are respectively divalent and trivalent; the manganese is in +2 and +3 oxydation states.

Enrichment mechanisms of tellurium in ferromanganese crusts

NASA Astrophysics Data System (ADS)

Sakaguchi, A.; Sugiyama, T.; Usui, A.; Takahashi, Y.

2012-04-01

Marine ferromanganese crusts (FMCs) consist of iron (Fe) hydroxides and manganese (Mn) oxides with various minor and trace elements. Especially for tellurium (Te), which is recognized as one of the rare metals, it has been reported that this element is concentrated about 105 times in FMCs compared with earth's crust, and the host phase might be Fe (oxy)hydroxide (Hein et al., 2003). Actually, in our previous study, the high concentration of Te in very surface layers of FMCs was found from the top to halfway down of a seamount in the Pacific Ocean. However, the concentration of Te in surface layers through the seamount showed good correlation with that of Mn instead of Fe. In this study, we attempted to clarify the enrichment mechanism of Te in FMCs with some methods including X-ray absorption fine structure (XAFS) technique for synthesised /natural samples. Seventeen FMC samples were collected from the Takuyo-Daigo seamount, from 950 m (summit) to 3000 m in water depth, with hyper-dolphin (remotely operated vehicle) equipped with live video camera and manipulators. The growth rates of all FMC samples were estimated to be about 3 mm/Ma. Very surface layer (less than 1 mm) of all FMC was analyzed with XRD and XAFS to confirm the mineral composition and speciation of Te. Furthermore, to serve as an aid to clarify the adsorption mechanism of Te on FMCs, distribution coefficients (Kd) and oxidation states were determined through the adsorption experiments of Te(IV) and Te(VI) on ferrihydrite and δ-MnO2. In all the experiments, pH and ionic strength were adjusted to pH 7.5 and 0.7 M, respectively. The oxidation state of Te in water phase was determined with HPLC-ICP-MS. As for the analysis of oxidation and adsorption states on the solid phase, XAFS was employed. The major mineral composition of Fe and Mn had no significant variation through the water depth of Takuyo-Daigo seamount. The oxidation state of Te in all samples showed hexavalent, and there was no significant difference of adsorption state independent of the DO, salinity and temperature in water. It has been reported that Te exists as tetravalent and hexavalent in sea water of the Pacific Ocean (Nozaki, 1996). Thus, it can be said that the Te in sea water is oxidised and incorporated into FMCs. As a result of the adsorption experiments in laboratory, the Kd of Te on ferrihydrite was larger than that of δ-MnO2, and Te(IV) was adsorbed to a larger degree than Te(VI) on both minerals. The adsorption experiments of Te(IV) on δ-MnO2 showed that the solid phase has only hexavalent Te, although the water phase has both tetra and hexavalent species of Te. Te(IV) on ferrihydrite was not oxidized to Te(VI). From these results, it can be suggested that Te(IV) was oxidized by δ-MnO2 and would be adsorbed onto ferrihydrite. Actually, the results of double-cell adsorption experiments support this hypothesis. The detail of our results and discussion will be given in the presentation.

The influence of curcumin and manganese complex of curcumin on cadmium-induced oxidative damage and trace elements status in tissues of mice.

PubMed

Eybl, Vladislav; Kotyzová, Dana; Lesetický, Ladislav; Bludovská, Monika; Koutenský, Jaroslav

2006-01-01

Curcumin (diferuoyl methane) from turmeric is a well-known biologically active compound. It has been shown to ameliorate oxidative stress and it is considered to be a potent cancer chemopreventive agent. In our previous study the antioxidative effects of curcumin in cadmium exposed animals were demonstrated. Also manganese exerts protective effects in experimental cadmium intoxication. The present study examined the ability of the manganese complex of curcumin (Mn-curcumin) and curcumin to protect against oxidative damage and changes in trace element status in cadmium-intoxicated male mice. Curcumin or Mn-curcumin were administered at equimolar doses (0.14 mmol/kg b.w.) for 3 days, by gastric gavages, dispersed in methylcellulose. One hour after the last dose of antioxidants, cadmium chloride (33 micromol/kg) was administered subcutaneously. Both curcumin and Mn-curcumin prevented the increase of hepatic lipid peroxidation -- expressed as MDA level, induced by cadmium intoxication and attenuated the Cd-induced decrease of hepatic GSH level. No change in hepatic glutathione peroxidase or catalase activities was found in Cd-exposed mice. A decreased GSH-Px activity was measured in curcumin and Mn-curcumin alone treated mice. Neither curcumin nor Mn-curcumin treatment influenced cadmium distribution in the tissues and did not correct the changes in the balance of essential elements caused by Cd-treatment. The treatment with Mn-curcumin increased the Fe and Mn content in the kidneys of both control and Cd-treated mice and Fe and Cu content in the brain of control mice. In conclusion, regarding the antioxidative action, introducing manganese into the curcumin molecule does not potentiate the studied effects of curcumin. Copyright 2006 John Wiley & Sons, Ltd.

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines.

PubMed

Modin, Hanna; Persson, Kenneth M; Andersson, Anna; van Praagh, Martijn

2011-05-30

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of Mn and Fe on the Formation of Fe- and Mn-Rich Intermetallics in Al-5Mg-Mn Alloys Solidified Under Near-Rapid Cooling.

PubMed

Liu, Yulin; Huang, Gaoren; Sun, Yimeng; Zhang, Li; Huang, Zhenwei; Wang, Jijie; Liu, Chunzhong

2016-01-29

Mn was an important alloying element used in Al-Mg-Mn alloys. However, it had to be limited to a low level (<1.0 wt %) to avoid the formation of coarse intermetallics. In order to take full advantage of the benefits of Mn, research was carried out to investigate the possibility of increasing the content of Mn by studying the effect of cooling rate on the formation of Fe- and Mn-rich intermetallics at different content levels of Mn and Fe. The results indicated that in Al-5Mg-Mn alloy with low Fe content (<0.1 wt %), intermetallic Al₆(Fe,Mn) was small in size and amount. With increasing Mn content, intermetallic Al₆(Fe,Mn) increased, but in limited amount. In high-Fe-containing Al-5Mg-Mn alloys (0.5 wt % Fe), intermetallic Al₆(Fe,Mn) became the dominant phase, even in the alloy with low Mn content (0.39 wt %). Cooling rate played a critical role in the refinement of the intermetallics. Under near-rapid cooling, intermetallic Al₆(Fe,Mn) was extremely refined. Even in the high Mn and/or high-Fe-containing alloys, it still demonstrated fine Chinese script structures. However, once the alloy composition passed beyond the eutectic point, the primary intermetallic Al₆(Fe,Mn) phase displayed extremely coarse platelet-like morphology. Increasing the content of Fe caused intermetallic Al₆(Fe,Mn) to become the primary phase at a lower Mn content.

Efficient oxidation and sorption of arsenite using a novel titanium(IV)-manganese(IV) binary oxide sorbent.

PubMed

Zhang, Wei; Liu, Caihong; Zheng, Tong; Ma, Jun; Zhang, Gaosheng; Ren, Guohui; Wang, Lu; Liu, Yulei

2018-04-19

Owing to the high toxicity and mobility, the removal of arsenite (As(III)) is significantly more difficult than arsenate (As(V)), thus representing a major challenge in arsenite-contaminated water treatment. For efficient elimination of As(III), we successfully fabricated a novel Ti-Mn binary oxide via a simultaneous oxidation and coprecipitation process. The amorphous oxide was aggregated from nanosized particles with a high specific surface area of 349.5 m 2 /g. It could effectively oxidize As(III) to As(V) and had a high As(III) sorption capacity of 107.0 mg/g. As(III) sorption occurred rapidly and equilibrium was achieved within 24 h. The kinetic data was well fitted by the pseudo-second-order equation, indicating a chemical sorption process. The material was almost independent upon the presence of competitive ions. The As(III) removal by the sorbent is a combined process coupled oxidation with sorption, where the MnO 2 content is mainly responsible for oxidizing As(III) to As(V) and the formed As(V) is then adsorbed onto the surface of amorphous TiO 2 content, through replacing the surface hydroxyl group or the adsorbed As(III) and forming inner-sphere surface complexes. Furthermore, the arsenic-containing oxide could be effectively regenerated and reused. The bi-functional sorbent could be used as a potentially attractive sorbent for As(III) removal in drinking water treatment and environmental remediation. Copyright © 2018. Published by Elsevier B.V.

Effects of inorganic electron acceptors on methanogenesis and methanotrophy and on the community structure of bacteria and archaea in sediments of a boreal lake

NASA Astrophysics Data System (ADS)

Rissanen, Antti J.; Karvinen, Anu; Nykänen, Hannu; Peura, Sari; Tiirola, Marja; Mäki, Anita; Kankaala, Paula

2016-04-01

Lake sediments are globally significant sources of CH4 to the atmosphere, but the factors controlling the production and consumption of CH4 in these systems are understudied. Increasing availability of electron acceptors (EA) (other than CO2) in sediments can decrease or even suppress CH4 production by diverting the electron flow (from H2 and organic substances) from methanogenic to other anaerobic respiration pathways. However, whether these changes in microbial function extend down to changes in the structure of microbial communities is not known. Also anaerobic oxidation of methane (AOM) could be enhanced by increased availability of EAs (SO42-, NO3-, Fe3+ and Mn4+), but information on the role of this process in lake sediments is scarce. We studied the effects of inorganic EAs on the potential for CH4 production and consumption and on the structure of microbial communities in sediments of a boreal lake. Anoxic slurries of sediment samples collected from two depths (0 - 10 cm; 10 - 30 cm) of the profundal zone of a boreal, mesotrophic Lake Ätäskö, were amended with 1) CH4 or with CH4 and either 2) 10 mM Mn4+, 3) 10 mM Fe3+, 4) O2 or 5) CH2F2 (inhibitor of aerobic methane oxidation) and incubated at +10° C for up to 4 months. Furthermore, slurries from the 10 - 30 cm layer were amended with CH4 and either 6) 2 mM NO3- or 7) 2 mM SO42- and incubated at +4 ° C for up to 14 months. The processes were measured using 13C-labelling and by concentration measurements of CH4 and CO2. Effects of treatments 1-3 on microbial communities were also analysed by next-generation sequencing of 16S rRNA, as well as methyl coenzyme-M reductase gene amplicons and mRNA transcripts. CH4 production (max. 83 nmol gdw-1d-1) took place in the anaerobic treatments but was generally decreased by the addition of NO3-, SO42-, Fe3+ and Mn4+. Although the structure of sediment archaeal community was resistant to Fe3+/Mn4+ - additions, slight changes in the structure of bacterial community occurred. Besides decreasing the availability of methanogenic substrates, the Mn4+/Fe3+ - induced changes in the bacterial community also probably decreased the H2:acetate - ratio in the substrate pool. This led to increase in the relative activity (mRNA level) of some operational taxonomic units assigned to aceticlastic Methanosaetaceae and decrease in the relative activity of hydrogenotrophic Methanoregulaceae in the sediment. CH4 oxidation (0.02 - 0.30 nmol gdw-1d-1 in anaerobic and 18 - 73 nmol gdw-1d-1in aerobic treatments) took place without EA additions and was enhanced only by O2. This suggests decoupling of the process from the reduction of other inorganic EAs. The results also indicate that Fe3+/Mn4+ - reduction did not increase CH4 oxidation via increased availability of SO42- by cryptic sulfur cycle or via increased availability of organic EAs. Furthermore, ANME - archaea were only ≤ 3% of sediment archaeal community and their relative activity was decreased during incubations. Thus, EA driving CH4 oxidation in the anoxic sediments of the lake remains unknown or the process was methanogen-driven via trace methane oxidation.

Distribution and chemistry of suspended particles from an active hydrothermal vent site on the Mid-Atlantic Ridge at 26°N

NASA Astrophysics Data System (ADS)

Trocine, Robert P.; Trefry, John H.

1988-04-01

Suspended particles were collected from an area of active hydrothermal venting at the Trans-Atlantic Geotraverse (TAG) Hydrothermal Field on the Mid-Atlantic Ridge and analyzed for Fe, Mn, Cd, Zn, Cu, V, Ni, Cr, Pb, Mg, Ca, Al and Si. Rapid advection of vent-derived precipitates produced a lens with total suspended matter (TSM) loadings of 14-60 μg/l at 200-700 m above the seafloor; TSM concentrations > 60 μg/l were observed only at near-vent sites. The distribution of suspended particles correlated well with increased dissolved Mn concentrations and particulate Fe values near the vent source. Particulate Fe values decreased linearly relative to TSM concentrations as hydrothermal precipitates mixed with background suspended matter. Near-vent precipitates were characterized by up to 35% Fe, 2% Zn, 0.6% Cu and > 100 μg/g Cd. In comparison to Fe, particulate Cd, Zn and Cu values decreased dramatically away from the vent source. This trend supports differential settling and/or dissolution of Cd-, Zn- and Cu-bearing phases. Particulate Mn and Fe values were inversely related with only 50 μg Mn/g in the near-vent particles. At near-vent sites, > 99% of the total Mn was in solution; this fraction decreased to 75-80% at background TSM values. In contrast to Cd, Zn and Cu, particulate V levels show a continuous, linear decrease with particulate Fe values. This trend is explained by adsorption of V on Fe-oxides in the vent plume. Scavenging of Cr, Pb and Mg by hydrothermal precipitates is also suggested by the data. Nickel and Al values were low in near-vent particles at < 100 and < 3 μg/g, respectively. The complementary behavior of dissolved Mn and particulate trace metals provides a useful framework for studying broad aspects of hydrothermal plume processes.

Cation hydrolysis and the regulation of trace metal composition in seawater

NASA Astrophysics Data System (ADS)

Kumar, M. Dileep

1987-08-01

Thermodynamic calculations have been performed for cation hydrolysis, including temperatures from 2°C to the high values of significance near Mid-Oceanic Ridge Systems (MORS). Eighteen elements with wide range of residence times ( t) in seawater (Mn, Th, Al, Bi, Ce, Co, Cr(III), Fe, Nd, Pb, Sc, Sm, Ag, Cd, Cu, Hg, Ni and Zn) have been considered. A model for the regulation of trace metal composition in seawater by cation hydrolytic processes, including those at MORS, is presented. Results show an increase in the abundance of neutral metal hydroxyl species with increase in temperature. During hydrothermal mixing, as the temperature increases, transformation from lower positive hydroxyl complexes to higher or neutral complexes would occur for Cd, Ce, Co, Cr(III), Cu, Mn, Nd, Ni, Pb, Sm and Zn. pH values for adsorption of the metal ion onto solid surfaces have direct relation with pH values of hydrolysis. Co, Mn and Pb could be oxidized to higher states (at Mn-oxide surfaces) that would occur even at MORS. Ce can also be oxidized at 25°C. Solubility calculations show that Al, Bi, Cr(III), Sc, Fe and Th are saturated while Ce, Nd and Sm are not with respect to their oxyhydroxide solids at their concentrations in seawater at 25°C. Cu, Hg, Ni and Zn reach saturation equilibrium at 250°C, whereas Co, Mn and Pb exhibit unsaturation. The results suggest an increase in scavenging capacity of a cation with rise in temperature.

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River.

PubMed

Hoque, Raza Rafiqul; Goswami, K G; Kusre, B C; Sarma, K P

2011-06-01

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe-Mn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.

Fractionation of silver isotopes in native silver explained by redox reactions

NASA Astrophysics Data System (ADS)

Mathur, Ryan; Arribas, Antonio; Megaw, Peter; Wilson, Marc; Stroup, Steven; Meyer-Arrivillaga, Danilo; Arribas, Isabel

2018-03-01

Scant data exist on the silver isotope composition of native silver specimens because of the relative newness of the technique. This study increases the published dataset by an order of magnitude and presents 80 silver new isotope analyses from native silver originating from a diverse set of worldwide deposits (8 deposit types, 33 mining districts in five continents). The measured isotopic range (defined as δ109Ag/107Ag in per mil units compared to NIST 978 Ag isotope standard) is +2.1 to -0.86‰ (2σ errors less than 0.015); with no apparent systematic correlations to date with deposit type or even within districts. Importantly, the data centering on 0‰ all come from high temperature hypogene/primary deposits whereas flanking and overlapping data represent secondary supergene deposits. To investigate the causes for the more fractionated values, several laboratory experiments involving oxidation of silver from natural specimens of Ag-rich sulfides and precipitation and adsorption of silver onto reagent grade MnO2 and FeOOH were conducted. Simple leach experiments demonstrate little Ag isotope fractionation occurred through oxidation of Ag from native Ag (Δsolution-native109Ag = 0.12‰). In contrast, significant fractionation occurred through precipitation of native Ag onto MnO2 (up to Δsolution-MnO2109Ag = 0.68‰, or 0.3amu). Adsorption of silver onto the MnO2 and FeOOH did not produce as large fractionation as precipitation (mean value of Δsolution-MnO2109Ag = 0.10‰). The most likely cause for the isotopic variations seen relates to redox effects such as the reduction of silver from Ag (I) to Ag° that occurs during precipitation onto the mineral surface. Since many Ag deposits have halos dominated by MnO2 and FeOOH phases, potential may exist for the silver isotope composition of ores and surrounding geochemical haloes to be used to better understand ore genesis and potential exploration applications. Aside from the Mn oxides, surface fluid silver isotope compositions might provide information about geochemical reactions relevant to both environmental and hydrometallurgical applications.

Influence of the insertion of a nano-oxide layer on the interfacial magnetism of FeMn /NiFe/Cu/NiFe spin valves

NASA Astrophysics Data System (ADS)

Tafur, Miguel; Alayo, W.; Munayco, P.; Baggio-Saitovitch, E.; Nascimento, V. P.; Alvarenga, A. D.; Brewer, W. D.

2007-05-01

We have studied the influence of an inserted nano-oxide layer (NOL) on the interfacial magnetism in spin-valve systems showing the giant magnetoresistance effect. Specifically, we performed a magnetic depth profile of these structures with and without a NOL, using the x-ray magnetic circular dichroism technique. We found that insertion of a NOL into the spin-valve structure is correlated with a stronger reduction of the magnetic moments at the ferromagnetic (FM)/NOL/FM interface in comparison with a spin valve without NOL.

Oxidative removal of aqueous steroid estrogens by manganese oxides.

PubMed

Xu, Lei; Xu, Chao; Zhao, Meirong; Qiu, Yuping; Sheng, G Daniel

2008-12-01

This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO2) and the factors influencing the reactions. Using 1 x 10(-5)M MnO2 at pH 4, estrone (E1), 17beta-estradiol (E2), estriol (E3) and 17alpha-ethinylestradiol (EE2), all at 4 x 10(-6)M, were rapidly removed within 220 min, indicating the effectiveness of MnO2 as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO2 and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO2 reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO2. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl2 in solutions containing 1 mg l(-1) humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g(-1). An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO2. Synthetic MnO2 is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO2 oxidation may be properly used to further enhance the MnO2 performance.

Bicarbonate requirement for the water-oxidizing complex of photosystem II.

PubMed

Klimov, V V; Baranov, S V

2001-01-05

It is well established that bicarbonate stimulates electron transfer between the primary and secondary electron acceptors, Q(A) and Q(B), in formate-inhibited photosystem II; the non-heme Fe between Q(A) and Q(B) plays an essential role in the bicarbonate binding. Strong evidence of a bicarbonate requirement for the water-oxidizing complex (WOC), both O2 evolving and assembling from apo-WOC and Mn2+, of photosystem II (PSII) preparations has been presented in a number of publications during the last 5 years. The following explanations for the involvement of bicarbonate in the events on the donor side of PSII are considered: (1) bicarbonate serves as an electron donor (alternative to water or as a way of involvement of water molecules in the oxidative reactions) to the Mn-containing O2 center; (2) bicarbonate facilitates reassembly of the WOC from apo-WOC and Mn2+ due to formation of the complexes MnHCO3+ and Mn(HCO3)2 leading to an easier oxidation of Mn2+ with PSII; (3) bicarbonate is an integral component of the WOC essential for its function and stability; it may be considered a direct ligand to the Mn cluster; (4) the WOC is stabilized by bicarbonate through its binding to other components of PSII.

Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Lei; Zhang, Yan; Hudak, Bethany M.

This report describes a new route to synthesize single-crystalline manganese-containing spinel nanowires (NWs) by a two-step hydrothermal and solid-state synthesis. Interestingly, a nanowire or nanorod morphology is maintained during conversion from MnO{sub 2}/MnOOH to CuMn{sub 2}O{sub 4}/Mg{sub 2}MnO{sub 4}, despite the massive structural rearrangement this must involve. Linear sweep voltammetry (LSV) curves of the products give preliminary demonstration that CuMn{sub 2}O{sub 4} NWs are catalytically active towards the oxygen evolution reaction (OER) in alkaline solution, exhibiting five times the magnitude of current density found with pure carbon black. - Highlights: • Synthesis of single-crystalline manganese-containing spinel nanowires. • Binary oxidemore » nanowire converted to ternary oxide wire through solid state reaction. • Approach to structure conversion with shape retention could be generally applicable. • Copper and Manganese display multiple oxidation states with potential for catalysis. • CuMn{sub 2}O{sub 4} nanowires show promise as catalysts for the oxygen evolution reaction.« less

Sulfur, sulfides, oxides and organic matter aggregated in submarine hydrothermal plumes at 9°50‧N East Pacific Rise

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.

Effect of Mn and Fe on the Formation of Fe- and Mn-Rich Intermetallics in Al–5Mg–Mn Alloys Solidified Under Near-Rapid Cooling

PubMed Central

Liu, Yulin; Huang, Gaoren; Sun, Yimeng; Zhang, Li; Huang, Zhenwei; Wang, Jijie; Liu, Chunzhong

2016-01-01

Mn was an important alloying element used in Al–Mg–Mn alloys. However, it had to be limited to a low level (<1.0 wt %) to avoid the formation of coarse intermetallics. In order to take full advantage of the benefits of Mn, research was carried out to investigate the possibility of increasing the content of Mn by studying the effect of cooling rate on the formation of Fe- and Mn-rich intermetallics at different content levels of Mn and Fe. The results indicated that in Al–5Mg–Mn alloy with low Fe content (<0.1 wt %), intermetallic Al6(Fe,Mn) was small in size and amount. With increasing Mn content, intermetallic Al6(Fe,Mn) increased, but in limited amount. In high-Fe-containing Al–5Mg–Mn alloys (0.5 wt % Fe), intermetallic Al6(Fe,Mn) became the dominant phase, even in the alloy with low Mn content (0.39 wt %). Cooling rate played a critical role in the refinement of the intermetallics. Under near-rapid cooling, intermetallic Al6(Fe,Mn) was extremely refined. Even in the high Mn and/or high-Fe-containing alloys, it still demonstrated fine Chinese script structures. However, once the alloy composition passed beyond the eutectic point, the primary intermetallic Al6(Fe,Mn) phase displayed extremely coarse platelet-like morphology. Increasing the content of Fe caused intermetallic Al6(Fe,Mn) to become the primary phase at a lower Mn content. PMID:28787888

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Ming, Douglas W.; Gellert, Ralf; Clark, Benton C.; Morris, Richard V.; Yen, Albert S.; Arvidson, Raymond E.; Crumpler, Larry S.; Farrand, William H.; Grant, John A.;

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Astrophysics Data System (ADS)

Ming, D. W.; Mittlefehldt, D. W.; Gellert, R.; Clark, B. C.; Morris, R. V.; Yen, A. S.; Arvidson, R. E.; Crumpler, L. S.; Farrand, W. H.; Grant, J. A., III; Jolliff, B. L.; Parker, T. J.; Peretyazhko, T.

2014-12-01

Mars Exploration Rover Opportunity is exploring Noachian age rocks of the rim of 22 km diameter Endeavour crater. Overlying the pre-impact lithologies and rim breccias is a thin apron of fine-grained sediments, the Grasberg fm, forming annuli on the lower slopes of rim segments. Hesperian Burns fm sandstones overly the Grasberg fm. Grasberg rocks have major element compositions that are distinct from Burns fm sandstones, especially when comparing interior compositions exposed by the Rock Abrasion Tool. Grasberg rocks are also different from Endeavour rim breccias, but have general compositional similarities to them. Grasberg sediments are plausibly fine-grained materials derived from the impact breccias. Veins of CaSO4 transect Grasberg fm rocks demonstrating post-formation aqueous alteration. Minor/trace elements show variations consistent with mobilization by aqueous fluids. Grasberg fm rocks have low Mn and high Fe/Mn ratios compared to the other lithologies. Manganese likely was mobilized and removed from the Grasberg host rock by redox reactions. We posit that Fe2+ from acidic solutions associated with formation of the Burns sulfate-rich sandstones acted as an electron donor to reduce more oxidized Mn to Mn2+. The Fe contents of Grasberg rocks are slightly higher than in other rocks suggesting precipitation of Fe phases in Grasberg materials. Pancam spectra show that Grasberg rocks have a higher fraction of ferric oxide minerals than other Endeavour rim rocks. Solutions transported Mn2+ into the Endeavour rim materials and oxidized and/or precipitated it in them. Grasberg has higher contents of the mobile elements K, Zn, Cl, and Br compared to the rim materials. Similar enrichments of mobile elements were measured by the Spirit APXS on West Spur and around Home Plate in Gusev crater. Enhancements in these elements are attributed to interactions of hydrothermal acidic fluids with the host rocks. Interactions of fluids with the Grasberg fm postdate the genesis of the Endeavour rim phyllosilicates. The aqueous alteration history of Endeavour rim rocks is complicated by different styles of alteration that have spanned the Noachian and Hesperian. Late stage acidic aqueous alteration of Grasberg fm materials is likely penecontemporaneous with the diagenesis of the sulfate-rich sediments of Meridiani Planum.

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites

NASA Technical Reports Server (NTRS)

Sutter, B.; Hossner, L. R.; Ming, D. W.

2005-01-01

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

SEM observation on microbial like structure in the ferromanganese crust from the western Pacific Magellan Seamount

NASA Astrophysics Data System (ADS)

Yang, K.; Park, H.; Baik, H.; Kim, J.; Park, K. R.; Yoon, J.; Kim, J. W.

2016-12-01

Understanding the biogeochemical process in the Fe-Mn crust layer is important to reconstruct the paleo-environment when the Fe-Mn crust layer forms. Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Electron Energy Loss Spectroscopy (EELS), and Polymerase Chain Reaction (PCR) were utilized to determine the redox states of Fe/Mn and microbial diversity at each layer. Samples were dredged from the western Pacific Magellan Seamount (OSM11) that consists of five well-defined layers from the rim (L1) to the core (L5). Some microbial like structures of sheath-like with filaments (L1 - L3), capsule-shaped (L2), fossilized coccolith mounds with phosphatized globules (L4), and bean-shaped (L4) were detected in entire layers. The cross sectional observation of bean-shaped microbe like structures encrusted with Fe-vernadite (L3) by Scanning Transmission Electron Microscopy (STEM) and Focused Ion Beam (FIB) technique revealed 1-μm diameter cavity in the center and porous structures of encrusting Fe-vernadite in periphery. Moreover, the organic carbon in the center cavity compared with inorganic C (from carbonate) in periphery was differentiated by C-K edge EELS spectra, suggesting that the microbe used to occupy. Indeed, the PCR analysis indicated the presence of functional gene (cumA; 1056bp & coxC; 810bp) association with Mn & Fe oxidizer that promote the formation of the crust. The cloning and sequencing of DNA PCR fragments revealed the appearance of geobacter species in L3 (G. sulfurreducens and G. lovleyi). The DNA molecular biological analysis and SEM direct observations suggest the evidence of biotic process in the formation of Fe-Mn crust.

Iron and Manganese Pyrophosphates as Cathodes for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hui; Upreti, Shailesh; Chernova, Natasha A.

2015-10-15

The mixed-metal phases, (Li{sub 2}Mn{sub 1-y}Fe{sub y}P{sub 2}O{sub 7}, 0 {le} y {le} 1), were synthesized using a 'wet method', and found to form a solid solution in the P2{sub 1}/a space group. Both thermogravimetric analysis and magnetic susceptibility measurements confirm the 2+ oxidation state for both the Mn and Fe. The electrochemical capacity improves as the Fe concentration increases, as do the intensities of the redox peaks of the cyclic voltammogram, indicating higher lithium-ion diffusivity in the iron phase. The two Li{sup +} ions in the three-dimensional tunnel structure of the pyrophosphate phase allows for the cycling of moremore » than one lithium per redox center. Cyclic voltammograms show a second oxidation peak at 5 V and 5.3 V, indicative of the extraction of the second lithium ion, in agreement with ab initio computation predictions. Thus, electrochemical capacities exceeding 200 Ah/kg may be achieved if a stable electrolyte is found.« less

Net alkalinity and net acidity 2: Practical considerations

USGS Publications Warehouse

Kirby, C.S.; Cravotta, C.A.

2005-01-01

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of FeII/FeIII. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples. A meaningful "net" acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinitymeasured - Hot Aciditymeasured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H+ acidity and is not recommended. The use of net alkalinity = -Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinitymeasured - Aciditycalculated) is recommended with some cautions. ?? 2005 Elsevier Ltd. All rights reserved.

A comparative study on electrochemical cycling stability of lithium rich layered cathode materials Li1.2Ni0.13M0.13Mn0.54O2 where M = Fe or Co

NASA Astrophysics Data System (ADS)

Laisa, C. P.; Nanda Kumar, A. K.; Selva Chandrasekaran, S.; Murugan, P.; Lakshminarasimhan, N.; Govindaraj, R.; Ramesha, K.

2016-08-01

In this work we compare electrochemical cycling stability of Fe containing Li rich phase Li1.2Ni0.13Fe0.13Mn0.54O2 (Fe-Li rich) with the well-known Co containing Li rich composition Li1.2Ni0.13Co0.13Mn0.54O2 (Co-Li rich). During the first charge, the activation plateau corresponding to removal of Li2O from the structure is smaller (removal of 0.6 Li) in the case of Fe-Li rich compared to Co-Li rich composition (0.8 Li removal). Consequently, the Fe compound shows better capacity retention; for example, after 100 cycles Fe-Li rich compound exhibits 20% capacity degradation where as it is about 40% in the case of Co-Li rich phase. The electrochemical and microscopy studies support the fact that compared to Co-Li rich compound, the Fe-Li rich composition display smaller voltage decay and reduced spinel conversion. XPS studies on charged/discharged Fe-Li rich samples show participation of Fe+3/Fe+4 redox during electrochemical cycling which is further supported by our first principles calculations. Also the temperature dependent magnetic studies on charge-discharged samples of Fe-Li rich compound point out that magnetic behavior is sensitive to cation oxidation states and Ni/Li disorder.

Weathering fluxes to the Gulf of Mexico from the Pliocene to Holocene based on radiogenic isotopes

NASA Astrophysics Data System (ADS)

Portier, A. M.; Martin, E. E.; Hemming, S. R.; Thierens, M. M.; Raymo, M. E.

2014-12-01

Chemical weathering of the continents plays a key role in the global carbon cycle and delivers solutes to the ocean. Past studies, documented using radiogenic isotopes of detrital and seawater samples, show the intensity of weathering varies with climate over a range of time scales.. We analyzed Pb and Nd isotopic values of seawater extracted from dispersed Fe-Mn oxides, <2μm (clay) and <63μm (silt) detrital fractions of Pliocene to Holocene sediment from Gulf of Mexico ODP Site 625B to evaluate long term variations in weathering fluxes for three time slices: the Pliocene/early Pleistocene, Mid Pleistocene Transition (MPT), and late Pleistocene/Holocene. We also examine short term glacial/interglacial variations. Little variation is seen in Nd isotopes of detrital fractions with age, suggesting little change in the average age of material delivered to the Gulf. Seawater Nd values become less radiogenic over the Pleistocene, consistent with observed changes in Caribbean seawater. Pb isotopes of silt fractions are also relatively constant through time, but clay fractions are more radiogenic at the MPT and dispersed Fe-Mn oxides trend to more radiogenic values in the late Pleistocene. Consequently, the Pb isotopes of dispersed Fe-Mn oxides tend to be less radiogenic than the detrital fractions in samples older than 2000 ka and more radiogenic than the detrital fractions, particularly clays, at the MPT. This may reflect greater incongruent silicate weathering during the MPT, a change in weathering conditions that could be consistent with the Regolith Hypothesis. Over glacial/interglacial timescales, dispersed Fe-Mn oxides Pb isotopes become more radiogenic than detrital fractions, and clay fractions become more radiogenic than silt fractions, during glacial periods. However, all fractions have similar values during interglacials. This pattern is distinct from previous studies that found enhanced incongruent silicate weathering during warm intervals, but is consistent with recent work finding a correlation with carbonate content, whereby low carbonate during glacials at Site 625 corresponds to a greater offset between leachate and detrital Pb isotopes. Biases from "heavy mineral effects" and changes in circulation during periods of lower sea level also need to be considered.

Role of oxidative stress in multiparity-induced endothelial dysfunction.

PubMed

Tawfik, Huda E; Cena, Jonathan; Schulz, Richard; Kaufman, Susan

2008-10-01

Multiparity is associated with increased risk of cardiovascular disease. We tested whether multiparity induces oxidative stress in rat vascular tissue. Coronary arteries and thoracic aorta were isolated from multiparous and age-matched virgin rats. Relaxation to ACh and sodium nitroprusside (SNP) was measured by wire myography. We also tested the effect of the superoxide dismutase mimetic MnTE2PyP (30 microM), the NADPH oxidase inhibitor apocynin (10 microM), and the peroxynitrite scavenger FeTPPs (10 microM) on ACh-mediated relaxation in coronary arteries. Vascular superoxide anion was measured using the luminol derivative L-012 and nitric oxide (NO) generation by the Griess reaction. Multiparity reduced maximal response and sensitivity to ACh in coronary arteries [maximal relaxation (E(max)): multiparous 49+/-3% vs. virgins 95%+/-3%; EC(50): multiparous 135+/-1 nM vs. virgins 60+/-1 nM], and in aortic rings (E(max): multiparous 38+/-3% vs. virgins 79+/-4%; EC(50): multiparous 160+/-2 nM vs. virgins 90+/-3 nM). Coronary arteries from the two groups relaxed similarly to SNP. Superoxide anions formation was significantly higher in both coronary arteries (2.8-fold increase) and aorta (4.1-fold increase) from multiparous rats compared with virgins. In multiparous rats, incubation with MnTE2PyP, apocynin, and FeTPPs improved maximal relaxation to ACh (MnTE2PyP: 74+/-5%; vehicle: 41+/-5%; apocynin: 73+/-3% vs. vehicle: 41+/-3%; FeTPPs: 72+/-3% vs. vehicle: 46+/-3%) and increased sensitivity (EC(50): MnTE2PyP: 61+/-0.5 nM vs. vehicle: 91+/-1 nM; apocynin: 45+/-3 nM vs. vehicle: 91+/-6 nM; FeTPP: 131 +/- 2 nM vs. vehicle: 185+/-1 nM). Multiparity also reduced total nitrate/nitrite levels (multiparous: 2.5+/-2 micromol/mg protein vs. virgins: 7+/-1 micromol/mg protein) and endothelial nitric oxide synthase protein levels (multiparous: 0.53+/-0.1 protein/actin vs. virgins: 1.0+/-0.14 protein/actin). These data suggest that multiparity induces endothelial dysfunction through decreased NO bioavailability and increased reactive oxygen species formation.

Substrate specificity and copper loading of the manganese-oxidizing multicopper oxidase Mnx from Bacillus sp. PL-12.

PubMed

Butterfield, Cristina N; Tebo, Bradley M

2017-02-22

Manganese(ii) oxidation in the environment is thought to be driven by bacteria because enzymatic catalysis is many orders of magnitude faster than the abiotic processes. The heterologously purified Mn oxidase (Mnx) from marine Bacillus sp. PL-12 is made up of the multicopper oxidase (MCO) MnxG and two small Cu and heme-binding proteins of unknown function, MnxE and MnxF. Mnx binds Cu and oxidizes both Mn(ii) and Mn(iii), generating Mn(iv) oxide minerals that resemble those found on the Bacillus spore surface. Spectroscopic techniques have illuminated details about the metallo-cofactors of Mnx, but very little is known about their requirement for catalytic activity, and even less is known about the substrate specificity of Mnx. Here we quantify the canonical MCO Cu and persistent peripheral Cu bound to Mnx, and test Mnx oxidizing ability toward different substrates at varying pH. Mn(ii) appears to be the best substrate in terms of k cat , but its oxidation does not follow Michaelis-Menten kinetics, instead showing a sigmoidal cooperative behavior. Mnx also oxidizes Fe(ii) substrate, but in a Michaelis-Menten manner and with a decreased activity, as well as organic substrates. The reduced metals are more rapidly consumed than the larger organic substrates, suggesting the hypothesis that the Mnx substrate site is small and tuned for metal oxidation. Of biological relevance is the result that Mnx has the highest catalytic efficiency for Mn(ii) at the pH of sea water, especially when the protein is loaded with greater than the requisite four MCO copper atoms, suggesting that the protein has evolved specifically for Mn oxidation.

Redox-induced mobilization of copper, selenium, and zinc in deltaic soils originating from Mississippi (U.S.A.) and Nile (Egypt) River Deltas: A better understanding of biogeochemical processes for safe environmental management.

PubMed

Shaheen, Sabry M; Frohne, Tina; White, John R; DeLaune, Ron D; Rinklebe, Jörg

2017-01-15

Studies about the mobilization of potentially toxic elements (PTEs) in deltaic soils can be challenging, provide critical information on assessing the potential risk and fate of these elements and for sustainable management of these soils. The impact of redox potential (E H ), pH, iron (Fe), manganese (Mn), sulfate (SO 4 2- ), chloride (Cl - ), aliphatic dissolved organic carbon (DOC), and aromatic dissolved organic carbon (DAC) on the mobilization of copper (Cu), selenium (Se), and zinc (Zn) was studied in two soils collected from the Nile and Mississippi Rivers deltaic plains focused on increasing our understanding of the fate of these toxic elements. Soils were exposed to a range of redox conditions stepwise from reducing to oxidizing soil conditions using an automated biogeochemical microcosm apparatus. Concentrations of DOC and Fe were high under reducing conditions as compared to oxidizing conditions in both soils. The proportion of DAC in relation to DOC in solution (aromaticity) was high in the Nile Delta soil (NDS) and low in the Mississippi Delta soil (MDS) under oxidizing conditions. Mobilization of Cu was low under reducing conditions in both soils which was likely caused by sulfide precipitation and as a result of reduction of Cu 2+ to Cu 1+ . Mobilization of Se was high under low E H in both soils. Release of Se was positively correlated with DOC, Fe, Mn, and SO 4 2- in the NDS, and with Fe in the MDS. Mobilization of Zn showed negative correlations with E H and pH in the NDS while these correlations were non-significant in the MDS. The release dynamics of dissolved Zn could be governed mainly by the chemistry of Fe and Mn in the NDS and by the chemistry of Mn in the MDS. Our findings suggest that a release of Se and Zn occurs under anaerobic conditions, while aerobic conditions favor the release of Cu in both soils. In conclusion, the release of Cu, Se, and Zn under different reducing and oxidizing conditions in deltaic wetland soils should be taken into account due to increased mobilization and the potential environmental risks associated with food security in utilizing these soils for flooded agricultural and fisheries systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 for solid oxide fuel cell application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaur, Anshu, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com; Mohiddon, Md. Ahamad, E-mail: gauranshu20@gmail.com, E-mail: ahamed.vza@gmail.com; Prasad, Muvva D.

2016-05-23

The growth and oxidation study of pulsed laser deposited MnCo{sub 2}O{sub 4} protective layer on SS430 substrate for solid oxide fuel cell application is demonstrated. MnCo{sub 2}O{sub 4} has been achieved in three different ways including, deposition at higher substrate temperature (700°C), and deposition at room temperature on pre-oxidized and untreated SS430 substrate followed by annealing at 700°C for 2 hrs. X-ray diffraction and Raman spectroscopy has been applied to demonstrate the kind of phases developed in each case. These three samples were subjected to heat treatment at 750°C for 5 hr. The extent of undesired Fe{sub 2}O{sub 3} phasemore » formation in the post deposition heat treated samples is discussed based on Raman spectroscopic results.« less

Interaction of coal-derived synthesis gas impurities with solid oxide fuel cell metallic components

NASA Astrophysics Data System (ADS)

Marina, Olga A.; Pederson, Larry R.; Coyle, Christopher A.; Edwards, Danny J.; Chou, Yeong-Shyung; Cramer, Carolyn N.

Oxidation-resistant alloys find use as interconnect materials, heat exchangers, and gas supply tubing in solid oxide fuel cell (SOFC) systems, especially when operated at temperatures below ∼800 °C. If fueled with synthesis gas derived from coal or biomass, such metallic components could be exposed to impurities contained in those fuel sources. In this study, coupons of ferritic stainless steels Crofer 22 APU and SS 441, austenitic nickel-chromium superalloy Inconel 600, and an alumina-forming high nickel alloy alumel were exposed to synthesis gas containing ≤2 ppm phosphorus, arsenic and antimony, and reaction products were tested. Crofer 22 APU coupons coated with a (Mn,Co) 3O 4 protective layer were also evaluated. Phosphorus was found to be the most reactive. On Crofer 22 APU, the (Mn,Cr) 3O 4 passivation layer reacted to form an Mn-P-O product, predicted to be manganese phosphate from thermochemical calculations, and Cr 2O 3. On SS 441, reaction of phosphorus with (Mn,Cr) 3O 4 led to the formation of manganese phosphate as well as an Fe-P product, predicted from thermochemical calculations to be Fe 3P. Minimal interactions with antimony or arsenic in synthesis gas were limited to Fe-Sb and Fe-As solid solution formation. Though not intended for use on the anode side, a (Mn,Co) 3O 4 spinel coating on Crofer 22 APU reacted with phosphorus in synthesis gas to produce products consistent with Mn 3(PO 4) 2 and Co 2P. A thin Cr 2O 3 passivation layer on Inconel 600 did not prevent the formation of nickel phosphides and arsenides and of iron phosphides and arsenides, though no reaction with Cr 2O 3 was apparent. On alumel, an Al 2O 3 passivation layer rich in Ni did not prevent the formation of nickel phosphides, arsenides, and antimonides, though no reaction with Al 2O 3 occurred. This work shows that unprotected metallic components of an SOFC stack and system can provide a sink for P, As and Sb impurities that may be present in fuel gases, and thus complicate experimental studies of impurity interactions with the anode.

Training effect in specular spin valves

NASA Astrophysics Data System (ADS)

Ventura, J.; Araujo, J. P.; Sousa, J. B.; Veloso, A.; Freitas, P. P.

2008-05-01

Specular spin valves show an enhanced giant magnetoresistive (GMR) ratio due to specular reflection in nano-oxide layers (NOLs) formed by the partial oxidation of CoFe pinned and free layers. The oxides that form the (pinned layer) NOL were recently shown to antiferromagnetically order at Ttilde 175K . Here, we study the training effect (TE) in MnIr/CoFe/NOL/CoFe/Cu/CoFe/NOL/Ta specular spin valves in the 300-15 K temperature range. The exchange bias direction between the MnIr and CoFe layers impressed during annealing is taken as the positive direction. The training effect is observed in antiferromagnetic (AFM)/ferromagnetic (FM) exchange systems and related to the rearrangement of interfacial AFM spin structure with the number of hysteretic cycles performed (n) , resulting in the decrease of the exchange field (Hexch) . Here, in the studied specular spin valve, TE was only observed for T<175K and is thus related to the pinned layer NOL-AFM ordering and to the evolution of the corresponding spin structure with n . We show that FM spins that are strongly coupled to AFM domains do not align with the applied positive magnetic field (H) , giving rise to a residual MR at H≫0 . Such nonsaturating MR will be related with a spin-glass-like behavior of the interfacial magnetism induced by the nano-oxide layer. The observed dependence of the training effect on the field cooling procedure is also likely associated with the existence of different spin configurations available in the magnetically disordered oxide. Furthermore, anomalous magnetoresistance cycles measured after cooling runs under -500Oe are here related to induced NOL exchange bias/applied magnetic field misalignment. The temperature dependence of the training effect was obtained and fitted by using a recent theoretical model.

Distribution of inorganic species in two Antarctic cryptoendolithic microbial communities

NASA Technical Reports Server (NTRS)

Johnston, C. G.; Vestal, J. R.; Friedmann, E. I. (Principal Investigator)

1989-01-01

Chemical differences were noted between two Antarctic cryptoendolithic (hidden within rock) microenvironments colonized by different microbial communities. Microenvironments dominated by cyanobacteria (BPC) had a higher pH (pH 7-8) than those dominated by lichen (LTL) (pH 4.5-5.5). In order to understand the interactions between the microbiota and the inorganic environment, the inorganic environment was characterized. Water-soluble, carbonate-bound, metal-oxide, organically bound, and residual inorganic species were sequentially extracted from rock samples by chemical means. Each fraction was then quantified using inductively coupled plasma atomic emission spectrometry. BPC contained much more water-soluble and carbonate-bound Ca and Mg than LTL. Metal-oxide species of Al, Fe, and Mn were more abundant in LTL than BPC. Metal oxides appeared to be mobilized (in the order Mn > Fe > Al) from the LTL lichen zone but remained immobile in BPC sandstone. The distribution of K and P bound to metal oxide reflected the distribution of iron oxide in LTL, an indication of the importance of iron in controlling the availability of nutrients in this ecosystem. Metal oxides in turn were likely controlled or influenced by organic matter associated with the lichen community. Despite overall depletion of Fe, Al, and K in the lichen zone, SEM X-ray analysis showed that they were enriched in fungal hyphae. Water-soluble P was present despite the presence of metal oxides, which sequester phosphate. This has biological relevance since P is an essential nutrient.

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals

NASA Astrophysics Data System (ADS)

Feenstra, A.; Peters, Tjerk

1996-12-01

Solid solutions of (Fe,Mn)TiO3 were synthesized, mostly at 0.10 XMn intervals, at 1 bar, 900°C and log f O 2 = 17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with XMn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700 900°C and fixed f O 2 in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO2 and H2 gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO3 ilmenite, which is well described by an asymmetric Margules model with WH FeFeMn = 9.703 and WH FeMnMn = 23.234 kJ/mol, WS FeFeMn = 19.65 and WS FeMnMn = 22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (WG FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite.

Characterization of lignin and Mn peroxidases from Phanerochaete chrysosporium. Progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Long-term objectives are to elucidate the role and mechanism of the various isozymes in lignin biodegradation. Work is described on electrochemical studies on lignin and Mn peroxidases. This study was performed to investigate the structural aspects which confer the lignin and Mn peroxidases with their high reactivity. The experimentally determined redox potential of the Fe{sup 3+}/Fe{sup 2+} couple for the lignin peroxidase isozymes H1, H2, H8 and H10 are very similar, near-130 mV. The redox potential for the Mn peroxidase isozymes H3 and H4 are similar to each other ({minus}88 mV and {minus}95 mV, respectively) and are more positive thanmore » the lignin peroxidases. The higher redox potential for the Fe{sup 3+}/Fe{sup 2+} couple is consistent with the heme active site of these fungal peroxidases being more electron deficient. To investigate the accessibility of the heme active site to the substrate which is oxidized [veratryl alcohol and Mn (II)], we investigated whether these substrates had any affect on the redox potential of the heme. The E{sub m7} value for lignin and Mn peroxidases are not affected by their respective substrates, veratryl alcohol and Mn (II). These results suggest that substrates do not directly interact with the ferric heme-iron as axial ligands. This is consistent with the present model for peroxidase catalysis. Suicide inhibitor (1) and nmr studies (2) indicate that the heme-iron of horseradish peroxidase (HRP) is not fully accessible to bulky substrates occur at the periphery of the heme.« less

Structural characterization of nano-oxide layers in PtMn based specular spin valves

NASA Astrophysics Data System (ADS)

Zhou, Min; Chen, Lifan; Diao, Zhitao; Park, Chang-Man; Huai, Yiming

2005-05-01

A systematic structure characterization of nano-oxide layers (NOLs) and specular spin valves using x-ray diffraction and high-resolution transmission electron microscopy (HRTEM) has been studied. High-angle x-ray diffraction data show almost identical fcc textures for both natural and plasma NOL spin-valves. Low-angle x-ray reflectivity spectrum shows more deteriorated Kiessig fringes at high incident angles for natural oxide sample, indicating rougher interfaces in natural oxidation than in plasma oxidation. Oxygen exposure plays an important role in NOLs process. Fabricating NOLs without any crystal structure degradation is critical to obtain high MR ratio. HRTEM reveals that oxide clusters mixing with insufficiently oxidized CoFe layers prevailed in natural NOL, and the natural oxidation was inhomogeneous. In contrast, plasma NOL has a thinner, more homogeneously oxidized CoFe layers with sharp interfaces. In plasma NOLs, the structures still maintain CoFe crystal structure. The structures and magnetic correlation of the NOL specular spin valves are discussed.

Enhanced degradation of Orange G by permanganate with the employment of iron anode.

PubMed

Bu, Lingjun; Shi, Zhou; Zhou, Shiqing

2017-01-01

Iron anode was employed to enhance the degradation of Orange G (OG) by permanganate (EC/KMnO 4 ). Continuously generated Fe 2+ from iron anode facilitated the formation of fresh MnO 2 , which plays a role in catalyzing permanganate oxidation. The EC/KMnO 4 system also showed a better performance to remove OG than Fe 2+ /KMnO 4 , indicating the importance of in situ formed fresh MnO 2 . Besides, the effects of applied current, KMnO 4 dosage, solution pH, and natural organics were evaluated and results demonstrated that high current and oxidant dosage are favorable for OG removal. And the application of iron anode has a promoting effect on the KMnO 4 oxidation over a wide pH range (5.0-9.0), while the Fe 2+ /KMnO 4 process does not. For natural organics, its presence could inhibit OG removal due to its competitive role. And the promoting effect of OG removal by the EC/KMnO 4 process in natural water was confirmed. At last, the EC/KMnO 4 process showed a satisfying performance on the decolorization and mineralization of OG. This study provides a potential technology to enhance permanganate oxidation and broadens the knowledge of azo dye removal.

Ibitira: A basaltic achondrite from a distinct parent asteroid

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.

2004-01-01

I have done detailed petrologic study of Ibitira, nominally classified as a basaltic eucrite. The Fe/Mn ratio of Ibitira pyroxenes with <10 mole % wollastonite component is 36.4 0.4, and is well-resolved from those of five basaltic eucrites studied for comparison; 31.2-32.2. Data for the latter completely overlap. Ibitira pyroxenes have lower Fe/Mg than the basaltic eucrite pyroxenes. Thus, the higher Fe/Mn ratio does not reflect a simple difference in oxidation state. Ibitira also has an oxygen isotopic composition, alkali element contents and a Ti/Hf ratio that distinguish it from basaltic eucrites. These differences support derivation from a distinct parent asteroid. Ibitira is the first recognized representative of the fifth known asteroidal basaltic crust.

Stability Behavior and Thermodynamic States of Iron and Manganese in Sandy Soil Aquifer, Manukan Island, Malaysia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Chin Yik, E-mail: cy_lin_ars@hotmail.com; Abdullah, Mohd. Harun; Musta, Baba

2011-03-15

A total of 20 soil samples were collected from 10 boreholes constructed in the low lying area, which included ancillary samples taken from the high elevation area. Redox processes were investigated in the soil as well as groundwater in the shallow groundwater aquifer of Manukan Island, Sabah, Malaysia. Groundwater samples (n = 10) from each boreholes were also collected in the low lying area to understand the concentrations and behaviors of Fe and Mn in the dissolved state. This study strives to obtain a general understanding of the stability behaviors on Fe and Mn at the upper unsaturated and themore » lower-saturated soil horizons in the low lying area of Manukan Island as these elements usually play a major role in the redox chemistry of the shallow groundwater. Thermodynamic calculations using PHREEQC showed that the groundwater samples in the study area are oversaturated with respect to goethite, hematite, Fe(OH){sub 3} and undersaturated with respect to manganite and pyrochroite. Low concentrations of Fe and Mn in the groundwater might be probably due to the lack of minerals of iron and manganese oxides, which exist in the sandy aquifer. In fact, high organic matters that present in the unsaturated horizon are believed to be responsible for the high Mn content in the soil. It was observed that the soil samples collected from high elevation area (BK) comprises considerable amount of Fe in both unsaturated (6675.87 mg/kg) and saturated horizons (31440.49 mg/kg) compared to the low Fe content in the low lying area. Based on the stability diagram, the groundwater composition lies within the stability field for Mn{sup 2+} and Fe{sup 2+} under suboxic condition and very close to the FeS/Fe{sup 2+} stability boundary. This study also shows that both pH and Eh values comprise a strong negative value thus suggesting that the redox potential is inversely dependent on the changes of pH.« less

A Polar Corundum Oxide Displaying Weak Ferromagnetism at Room Temperature

PubMed Central

2012-01-01

Combining long-range magnetic order with polarity in the same structure is a prerequisite for the design of (magnetoelectric) multiferroic materials. There are now several demonstrated strategies to achieve this goal, but retaining magnetic order above room temperature remains a difficult target. Iron oxides in the +3 oxidation state have high magnetic ordering temperatures due to the size of the coupled moments. Here we prepare and characterize ScFeO3 (SFO), which under pressure and in strain-stabilized thin films adopts a polar variant of the corundum structure, one of the archetypal binary oxide structures. Polar corundum ScFeO3 has a weak ferromagnetic ground state below 356 K—this is in contrast to the purely antiferromagnetic ground state adopted by the well-studied ferroelectric BiFeO3. PMID:22280499

The magnetic field and the evolution of element spots on the surface of the HgMn eclipsing binary ARAur

NASA Astrophysics Data System (ADS)

Hubrig, S.; Savanov, I.; Ilyin, I.; González, J. F.; Korhonen, H.; Lehmann, H.; Schöller, M.; Granzer, T.; Weber, M.; Strassmeier, K. G.; Hartmann, M.; Tkachenko, A.

2010-10-01

The system ARAur is a young late B-type double-lined eclipsing binary with a primary star of HgMn peculiarity. We applied the Doppler imaging method to reconstruct the distribution of Fe and Y over the surface of the primary using spectroscopic time series obtained in 2005 and from 2008 October to 2009 February. The results show a remarkable evolution of the element distribution and overabundances. Measurements of the magnetic field with the moment technique using several elements reveal the presence of a longitudinal magnetic field of the order of a few hundred gauss in both stellar components and a quadratic field of the order of 8kG on the surface of the primary star. Based on observations obtained at the 2.56-m Nordic Optical Telescope on La Palma, the Karl-Schwarzschild-Observatorium in Tautenburg and the STELLA robotic telescope on Tenerife. E-mail: shubrig@aip.de

Electronic structure, magnetism and thermoelectricity in layered perovskites: Sr2SnMnO6 and Sr2SnFeO6

NASA Astrophysics Data System (ADS)

Khandy, Shakeel Ahmad; Gupta, Dinesh C.

2017-11-01

Layered structures especially perovskites have titanic potential for novel device applications and thanks to the multifunctional properties displayed in these materials. We forecast and justify the robust spin-polarized ferromagnetism in half-metallic Sr2SnFeO6 and semiconducting Sr2SnMnO6 perovskite oxides. Different approximation methods have been argued to put forward their physical properties. The intriguingly intricate electronic band structures favor the application of these materials in spintronics. The transport parameters like Seebeck coefficient, electrical and thermal conductivity, have been put together to establish their thermoelectric response. Finally, the layered oxides are found to switch their application as thermoelectric materials and hence, these concepts design the principles of the technologically desired thermoelectric and spin based devices.

Iron Cycling in Sediment of the North Atlantic: Preliminary Results from R/V Knorr Expedition 223

NASA Astrophysics Data System (ADS)

Anderson, C. H.; Estes, E. R.; Dyar, M. D.; Murray, R. W.; Spivack, A. J.; Sauvage, J.; McKinley, C. C.; Present, T. M.; Homola, K.; Pockalny, R. A.; D'Hondt, S.

2015-12-01

Iron (Fe) in marine sediments is a significant microbial electron acceptor [Fe(III)] in suboxic conditions and is an electron donor [Fe(II)] in oxic conditions. In the transition from oxic to suboxic sediment, a portion of solid Fe is reduced and mobilized as soluble Fe(II) into interstitial water during the oxidation of organic matter. The presence of Fe and its oxidation state in oxic sediment provides insight into an important metabolic and mineral reaction pathway in subseafloor sediment. We recovered bulk sediment and interstitial water at western North Atlantic sites during Expedition 223 on the R/V Knorr in November, 2014. The expedition targeted regions with predominantly oxic sediment and regions with predominantly anoxic sediment, ideal for investigating redox Fe cycling between solid and aqueous phases. At Site 10 (14.4008N, 50.6209W, 4455m water depth), interstitial dissolved oxygen is depleted within the upper few meters of sediment. At Site 12 (29.6767N, 58.3285W, 5637m water depth), interstitial dissolved oxygen is present throughout the cored sediment column (10s of meters). Here we present total solid Fe concentration for 45 bulk sediment samples and total aqueous Fe and Mn concentrations for 50 interstitial water samples analyzed via ICP-ES. We additionally present Fe(II) and Fe(III) speciation results from 10 solid sediment samples determined by Mossbauer spectroscopy. We trace downcore fluctuations in Fe in solid and aqueous phases to understand Fe cycling in oxic, suboxic, and transitional regimes. Our preliminary data indicate that solid Fe concentration ranges from 4-6 wt % at the oxic site; aqueous Fe ranges from below detection to 20μM and aqueous Mn ranges from 1 to 125 μM at the anoxic site. In the anoxic sediment (Site 10), 86-90% of the total Fe is oxidized [Fe(III)] and 10-14% as reduced [Fe(II)], compared to 3-6% as reduced [Fe(II)] at the oxic site (Site 12), even in sediment as old as 25 million years.

Chromium uptake by rice and accumulation in soil amended with municipal solid waste compost.

PubMed

Bhattacharyya, P; Chakraborty, A; Chakrabarti, K; Tripathy, S; Powell, M A

2005-09-01

Effect of addition of municipal solid waste compost (MSWC) on chromium (Cr) content of submerged rice paddies was studied. Experiments were conducted during the three consecutive wet seasons from 1997 to 1999 on rice grown under submergence, at the Experimental Farm of Calcutta University, India. A sequential extraction method was used to determine the various chromium fractions in MSWC and cow dung manure (CDM). Chromium was significantly bound to the organic matter and Fe and Mn oxides in MSWC and CDM. Chromium content in rice straw was higher than in rice grain. Chromium bound with organic matter in MSWC best correlated with straw Cr (r=0.99**) followed by Fe and Mn oxides (r=0.97*) and water soluble as well as exchangeable fractions (r=0.96*). The water soluble and the exchangeable fractions in MSWC best correlated with grain Cr (r=0.98*). The Cr content of rice grain had the highest correlation with water soluble and exchangeable Cr (r=0.99**) while the straw Cr best correlated with the Fe and Mn oxides (r=0.98*). Both the carbonate bound and residual fractions in MSWC and CDM did not significantly correlate with rice straw and grain Cr. MSWC would be a valuable resource for agriculture if it can be used safely, but long-term use may require the cessation of the dumping by the leather tanneries and other major contributors of pollutants.

Boxwork and ferromanganese coatings in hypogenic caves: An example from Sima de la Higuera Cave (Murcia, SE Spain)

NASA Astrophysics Data System (ADS)

Gázquez, Fernando; Calaforra, José-María; Rull, Fernando

2012-12-01

This paper examines the greyish-blue deposits that were recently discovered in the lower levels of the Sima de la Higuera Cave (Murcia, SE Spain) which occur as patinas over the walls and ceilings, as well as coating boxwork formations. Their mineralogy was determined using XRD and micro-Raman spectroscopy, while EDX microanalysis was used to determine their elemental composition. The mineralogical analyses revealed the presence of Mn oxides (todorokite and pyrolusite) and Fe with a low degree of crystallinity, whereas EDX microprobe showed elevated concentrations of Mn (38.2 wt.%), Fe (15.2 wt.%) and Pb (8.1 wt.%). The ferromanganese oxyhydroxides occur as botryoidal aggregates overlying blades of calcite that have a visibly sugary texture. The speleogenetic model proposed describes (1) an initial phase of precipitation of hydrothermal calcite veins (of hypogenic origin) within the fissures of the host rock under phreatic conditions and (2) a subsequent vadose phase involving preferential corrosion of the carbonate host rock caused by lowering of the pH resulting from CO2 diffusion in condensed water and oxidation of Fe and Mn under aerobic conditions, probably mediated by microorganisms. It is this later phase that gave rise to the boxwork. The boxwork of the Sima de la Higuera Cave is a singular example of a formation that is generated by dissolution-corrosion of the rock due to acidification caused by oxidation of iron and manganese.

Oxidations of alkenes and lignin model compounds in aqueous dispersions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Weiming.

1991-01-01

The objective was to develop methods to oxidize water-immiscible alkenes and lignin model compounds with polymer colloid supported transition metal catalysts. The oxidations of organic compounds were carried out in aqueous phase with several water-soluble oxidants and dioxygen. Cationic polymer latexes were prepared by the emulsion copolymerization of vinylbenzyl chloride, divinylbenzene, and vinyl octadecyl ether, or styrene, or n-decyl methacrylate, and the subsequent quaternization of copolymers with trimethylamine. The latex particles were 44 nm to 71 nm in diameter. The latex bound Mn porphyrin catalysts were formed with MnTSPP [TSPP = meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrin], which catalyzed the oxidation of cyclohexene, cycloocetene, allylbenzene,more » and 1-octene by sodium hypochlorite (NaOCl) and potassium peroxymonosulfate (KHSO[sub 5]). The latex bound porphyrin catalysts showed higher activity than MnTSPP in solution. Oxidations of 3,4-dimethoxybenzyl alcohol (DMBA), 4-hydroxy-3-methoxytoluene (HMT), and 3,4-dimethoxytoluene (DMT) were performed with either dioxygen or hydrogen peroxide and CoPcTS (PcTS = tetrasulfonatophthalocyanine), FePcTS, CuPcTS, NiPcTS, FeTCPP [TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin], and MnTSPP. CoPcTS catalyzed the autoxidation of DMBA and HMT at 70-85[degrees]C and pH [ge] 8. All catalysts were active for the oxidation of DMBA, HMT, and DMT with H[sub 2]O[sub 2]. Aqueous solutions of KHSO[sub 5] oxidized water-immiscible alkenes at room temperature in the absence of organic solvent. The acidic pH [le] 1.7 solutions of commercial 2KHSO[sub 5][center dot]K[sub 2]SO[sub 4] in water produced diols from all reactive alkenes except cyclooctene. Adjustment of initial pH to [ge]6.7 with NaHCO[sub 3] enabled selective epoxidations.« less

CoAs: The line of 3 d demarcation

NASA Astrophysics Data System (ADS)

Campbell, Daniel J.; Wang, Limin; Eckberg, Chris; Graf, Dave; Hodovanets, Halyna; Paglione, Johnpierre

2018-05-01

Transition metal-pnictide compounds have received attention for their tendency to combine magnetism and unconventional superconductivity. Binary CoAs lies on the border of paramagnetism and the more complex behavior seen in isostructural CrAs, MnP, FeAs, and FeP. Here we report the properties of CoAs single crystals grown with two distinct techniques along with density functional theory calculations of its electronic structure and magnetic ground state. While all indications are that CoAs is paramagnetic, both experiment and theory suggest proximity to a ferromagnetic instability. Quantum oscillations are seen in torque measurements up to 31.5 T and support the calculated paramagnetic Fermiology.

The effect of doping (Mn,B)3O4 materials as protective layers in different metallic interconnects for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Nó, María Luisa; Larrañaga, Aitor; Arriortua, María Isabel

2013-12-01

Spinel oxides with the general formula of (Mn,B)3O4 (B = Co, Fe) were used as barrier materials between the cathode and the metallic interconnect to reduce the rate of cathode degradation by Cr poisoning. The effect of doping at the B position was investigated terms of microstructure and electrical conductivity to determine its behaviour and effectiveness as a protective layer in contact with three metallic materials (Crofer 22 APU, SS430 and Conicro 4023 W 188). The analysis showed that the use of these materials considerably decreased the reactivity and diffusion of Cr between the cathode and the metallic interconnects. The protective layer doped with Fe at the B position exhibited the least amount of reactivity with the interconnector and cathode materials. The worst results were observed for SS430 cells coated with a protective layer perhaps due to their low Cr content. The Crofer 22 APU and Conicro 4023 W 188 samples exhibited very similar conductivity results in the presence of the MnCo1.9Fe0.1O4 protective coating. As a result, these two material combinations are a promising option for use as bipolar plates in SOFC.

Effects of sol-gel synthesis on 5Fe-15Mn-40Zn-40Ti-O mixed oxide structure and its H2S removal efficiency from industrial gas streams.

PubMed

Polychronopoulou, Kyriaki; Efstathiou, Angelos M

2009-06-15

A novel Fe-Mn-Zn-Ti-O mixed metal oxide has been developed for efficient low-temperature (25-50 degrees C) removal of H2S from a gas mixture containing 600 ppm H2S, 25 vol% H2, 7.5 vol % CO2, and 1-3 vol% H2O that simulates typical conditions experienced at the outlet of a bioreactor loaded with sulfate metal reducing bacteria (SMRB) that converts toxic Cr6+ and As5+ present in ground and surface waters and soils into nontoxic elements. During the latter conversion H2S gas is produced and has to be treated. In the present work it is demonstrated for the first time that by using the sol-gel synthesis route at given experimental conditions (e.g., metal precursor salts, solvent system, and solution pH), optimum structural properties for the Fe-Mn-Zn-Ti-O solid can be obtained for maximization of H2S uptake. In particular, at 25 degrees C an H2S uptake (0.085 g H2S/g solid) larger by at least a factor of 3 compared to a commercial Ni-based H2S absorbent material was obtained.

Effect of H2O on metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe: Implications for the oxidation state of the Earth and Mars

NASA Astrophysics Data System (ADS)

Clesi, V.; Bouhifd, M. A.; Bolfan-Casanova, N.; Manthilake, G.; Fabbrizio, A.; Andrault, D.

2016-11-01

This study investigates the metal-silicate partitioning of Ni, Co, V, Cr, Mn and Fe during core mantle differentiation of terrestrial planets under hydrous conditions. For this, we equilibrated a molten hydrous CI chondrite model composition with various Fe-rich alloys in the system Fe-C-Ni-Co-Si-S in a multi-anvil over a range of P, T, fO2 and water content (5-20 GPa, 2073-2500 K, from 1 to 5 log units below the iron-wüstite (IW) buffer and for XH2O varying from 500 ppm to 1.5 wt%). By comparing the present experiments with the available data sets on dry systems, we observes that the effect of water on the partition coefficients of moderately siderophile elements is only moderate. For example, for iron we observed a decrease in the partition coefficient of Fe (Dmet/silFe) from 9.5 to 4.3, with increasing water content of the silicate melt, from 0 to 1.44 wt%, respectively. The evolution of metal-silicate partition coefficients of Ni, Co, V, Cr, Mn and Fe are modelled based on sets of empirical parameters. These empirical models are then used to refine the process of core segregation during accretion of Mars and the Earth. It appears that the likely presence of 3.5 wt% water on Mars during the core-mantle segregation could account for ∼74% of the FeO content of the Martian mantle. In contrast, water does not play such an important role for the Earth; only 4-6% of the FeO content of its mantle could be due to the water-induced Fe-oxidation, for a likely initial water concentration of 1.8 wt%. Thus, in order to reproduce the present-day FeO content of 8 wt% in the mantle, the Earth could initially have been accreted from a large fraction (between 85% and 90%) of reducing bodies (similar to EH chondrites), with 10-15% of the Earth's mass likely made of more oxidized components that introduced the major part of water and FeO to the Earth. This high proportion of enstatite chondrites in the original constitution of the Earth is consistent with the 17O,48Ca,50Ti,62Ni and 90Mo isotopic study by Dauphas et al. (2014). If we assume that the CI-chondrite was oxidized during accretion, its intrinsically high water content suggests a maximum initial water concentration in the range of 1.2-1.8 wt% for the Earth, and 2.5-3.5 wt% for Mars.

Comparative study of the mechanical and tribological properties of a Hadfield and a Fermanal steel

NASA Astrophysics Data System (ADS)

Astudillo A., P. C.; Soriano G., A. F.; Barona Osorio, G. M.; Sánchez Sthepa, H.; Ramos, J.; Durán, J. F.; Pérez Alcázar, G. A.

2017-11-01

In this study, Fe-12.50Mn-1.10C-1.70Cr-0.40Mo-0.40Si-0.50(max)P-0.50(max)S (Hadfield alloy) and Fe-28.4Mn-0.86C-1.63Al-0.42Cu-1.80Mo-1.59Si-0.60W (Fermanal alloy) (Wt. %) in the aged condition were compared in terms of its tribological and microstructural properties. The x-ray diffraction (XRD) patterns were refined with the lines of the austenitic γ-phase, Chromium Iron Carbide (Cr2Fe14C), Iron Carbide (Fe2C), and Iron Oxide (Fe0.974O (II)) for the Hadfield alloy, and the lines of the austenitic γ-phase, martensite (M), Mn1.1Al0.9 phase and iron carbide (Fe7C3) for the Fermanal alloy. Mössbauer spectra were fit with two sites for the Hadfield alloy, which displayed as a broad singlet because of the austenitic disordered phase, and had a magnetic hyperfine field distribution, which corresponds to the Cr2Fe14C ferromagnetic carbides found by XRD. There were two paramagnetic sites, a singlet, which corresponds to the austenite disordered phase, and a doublet, which can be attributed to the Fe7C3 carbide. The obtained Rockwell C hardness for aged Hadfield and Fermanal alloys were 43.786 and 50.018 HRc, respectively.

Effect of Fe2+ and Mn2+ addition on growth and β-carotene production of Dunaliella salina

NASA Astrophysics Data System (ADS)

Mayasari, E.; Raya, I.; Natsir, H.

2018-03-01

Dunaliella salina is a unicellular chlorophyte, which could grow in a wide range of harsh environmental condition. Under growth-limitation conditions, D.salina was known as famous for a high β-carotene producer with up to 10% of its dry cell weights, therefore it could be a β-carotene supplement. The research aimed to find out the effect of Iron (Fe2+) and Manganese (Mn2+) towards β-carotene productivity as result of oxidative stress from the second photosystem (PS II). The analysis method was carried out by the ultrasonic extraction for short and cheap lyses of phytoplankton biomasses; infra-red (IR) to find out the interaction metal ion, and UV/VIS spectrophotometer to determine the β-carotene concentration from phytoplankton the crude extract. The result showed that the interaction occurred between metal ions and M-N, -O-M and M←OH-C groups in the amino acid of phytoplankton. The highest impact was indicated on 0.3 ppm Fe2+ to D. Salina. The highest β-carotene concentration was 13.08 μg/g DW for 0.3 ppm Fe2+ and 8.08 μg/g DW for 0.8 ppm Mn2+. The dry weight concentrations of β-carotene indicated that D. salina with 0.6 ppm Fe2+ addition had more potential as a β-carotene supplement.

Spin tuning of electron-doped metal-phthalocyanine layers.

PubMed

Stepanow, Sebastian; Lodi Rizzini, Alberto; Krull, Cornelius; Kavich, Jerald; Cezar, Julio C; Yakhou-Harris, Flora; Sheverdyaeva, Polina M; Moras, Paolo; Carbone, Carlo; Ceballos, Gustavo; Mugarza, Aitor; Gambardella, Pietro

2014-04-09

The spin state of organic-based magnets at interfaces is to a great extent determined by the organic environment and the nature of the spin-carrying metal center, which is further subject to modifications by the adsorbate-substrate coupling. Direct chemical doping offers an additional route for tailoring the electronic and magnetic characteristics of molecular magnets. Here we present a systematic investigation of the effects of alkali metal doping on the charge state and crystal field of 3d metal ions in Cu, Ni, Fe, and Mn phthalocyanine (Pc) monolayers adsorbed on Ag. Combined X-ray absorption spectroscopy and ligand field multiplet calculations show that Cu(II), Ni(II), and Fe(II) ions reduce to Cu(I), Ni(I), and Fe(I) upon alkali metal adsorption, whereas Mn maintains its formal oxidation state. The strength of the crystal field at the Ni, Fe, and Mn sites is strongly reduced upon doping. The combined effect of these changes is that the magnetic moment of high- and low-spin ions such as Cu and Ni can be entirely turned off or on, respectively, whereas the magnetic configuration of MnPc can be changed from intermediate (3/2) to high (5/2) spin. In the case of FePc a 10-fold increase of the orbital magnetic moment accompanies charge transfer and a transition to a high-spin state.

Environmental controls on biomineralization and Fe-mound formation in a low-temperature hydrothermal system at the Jan Mayen Vent Fields

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.

Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1−x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids

PubMed Central

Dell’Era, Alessandro; Pasquali, Mauro; Bauer, Elvira Maria; Lupi, Carla

2017-01-01

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1−x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1−x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1−x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material. PMID:29301206

Structural and mechanistic aspects of Mn-oxo and co-based compounds in water oxidation catalysis and potential applications in solar fuel production.

PubMed

Hou, Harvey J M

2010-08-01

To address the issues of energy crisis and global warming, novel renewable carbon-free or carbon-neutral energy sources must be identified and developed. A deeper understanding of photosynthesis is the key to provide a solid foundation to facilitate this transformation. To mimic the water oxidation of photosystem II oxygen evolving complex, Mn-oxo complexes and Co-phosphate catalytic material were discovered in solar energy storage. Building on these discoveries, recent advances in solar energy conversion showed a compelling working principle by combing the active Mn-oxo and Co-based catalysts in water splitting with semiconductor hetero-nanostructures for effective solar energy harnessing. In this review the appealing systems including Mn-oxo tetramer/Nafion, Mn-oxo dimer/TiO(2), Mn-oxo oligomer/WO(3), Co-Pi/Fe(2)O(3), and Co-Pi/ZnO are summarized and discussed. These accomplishments offer a promising framework and have a profound impact in the field of solar fuel production.

Vertical variation of potential mobility of heavy metal in sediment to groundwater of the Kanto plain, Japan

NASA Astrophysics Data System (ADS)

Hossain, S.; Hachinohe, S.; Ishiyama, T.; Hamamoto, H.; Oguchi, C. T.

2014-12-01

Heavy metals release from sediment may occur due to sediment water interaction under different changing environmental conditions. This has substantial influence on groundwater quality. However, identification of potentially mobile fractions of metals like Cu, Cr, Ni, Pb, Zn, Fe, Mn and Ti requires for the sustainable land and groundwater development and pollution management. 44 sediment and pore water samples at 1 m interval were analyzed from a vertical profile beneath the Naka river at the bottom of Central Kanto plain, Japan. Sequential extraction method was applied to determine potentially mobile forms of metals such as water soluble, ion exchangeable, acid soluble and Fe-Mn oxide bound. Metals were determined using X-Ray Fluorescence, Inductively coupled plasma atomic emission and mass spectrometer. Analyses show that potential mobility is high in river bed, volcanic ash mix, marine and transitional clayey silt. Metal mobility was higher in lower gravelly aquifer than upper sandy aquifer. Potential mobility and bioavailability of Zn, Cu, Ni, Pb and Mn are very high in river bed sediment which may pose threat to river bottom aquatic system. Zn, Cu and Ni concentration in pore water is high in river bed and peat bearing sediment. In pore water of marine and transitional sediment ion concentration such as Ca2+ and SO42- is very high indicating high mobility of Calcium and Sulfur from sediment as no significant variation observed in total content. In vertical profile, potential mobility tendency of metal in sediment trends to be Zn > Cu > Ni > Cr > Pb > Mn > Fe > Ti. Current study indicates low potential mobility and pollution risk to groundwater due to overall low metal concentration in pore water and high portion of metals attached with sediment as Fe-Mn oxide bound. More over under strong reducing condition considerable amount of metals will release and pollute groundwater.

Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

USGS Publications Warehouse

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.

The effect of iron to manganese substitution on microperoxidase 8 catalysed peroxidase and cytochrome P450 type of catalysis.

PubMed

Primus, J L; Boersma, M G; Mandon, D; Boeren, S; Veeger, C; Weiss, R; Rietjens, I M

1999-06-01

This study describes the catalytic properties of manganese microperoxidase 8 [Mn(III)MP8] compared to iron microperoxidase 8 [Fe(III)MP8]. The mini-enzymes were tested for pH-dependent activity and operational stability in peroxidase-type conversions, using 2-methoxyphenol and 3,3'-dimethoxybenzidine, and in a cytochrome P450-like oxygen transfer reaction converting aniline to para-aminophenol. For the peroxidase type of conversions the Fe to Mn replacement resulted in a less than 10-fold decrease in the activity at optimal pH, whereas the aniline para-hydroxylation is reduced at least 30-fold. In addition it was observed that the peroxidase type of conversions are all fully blocked by ascorbate and that aniline para-hydroxylation by Fe(III)MP8 is increased by ascorbate whereas aniline para-hydroxylation by Mn(III)MP8 is inhibited by ascorbate. Altogether these results indicate that different types of reactive metal oxygen intermediates are involved in the various conversions. Compound I/II, scavenged by ascorbate, may be the reactive species responsible for the peroxidase reactions, the polymerization of aniline and (part of) the oxygen transfer to aniline in the absence of ascorbate. The para-hydroxylation of aniline by Fe(III)MP8, in the presence of ascorbate, must be mediated by another reactive iron-oxo species which could be the electrophilic metal(III) hydroperoxide anion of microperoxidase 8 [M(III)OOH MP8]. The lower oxidative potential of Mn, compared to Fe, may affect the reactivity of both compound I/II and the metal(III) hydroperoxide anion intermediate, explaining the differential effect of the Fe to Mn substitution on the pH-dependent behavior, the rate of catalysis and the operational stability of MP8.

Local and average structure of Mn- and La-substituted BiFeO3

NASA Astrophysics Data System (ADS)

Jiang, Bo; Selbach, Sverre M.

2017-06-01

The local and average structure of solid solutions of the multiferroic perovskite BiFeO3 is investigated by synchrotron X-ray diffraction (XRD) and electron density functional theory (DFT) calculations. The average experimental structure is determined by Rietveld refinement and the local structure by total scattering data analyzed in real space with the pair distribution function (PDF) method. With equal concentrations of La on the Bi site or Mn on the Fe site, La causes larger structural distortions than Mn. Structural models based on DFT relaxed geometry give an improved fit to experimental PDFs compared to models constrained by the space group symmetry. Berry phase calculations predict a higher ferroelectric polarization than the experimental literature values, reflecting that structural disorder is not captured in either average structure space group models or DFT calculations with artificial long range order imposed by periodic boundary conditions. Only by including point defects in a supercell, here Bi vacancies, can DFT calculations reproduce the literature results on the structure and ferroelectric polarization of Mn-substituted BiFeO3. The combination of local and average structure sensitive experimental methods with DFT calculations is useful for illuminating the structure-property-composition relationships in complex functional oxides with local structural distortions.

Local and average structure of Mn- and La-substituted BiFeO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Bo; Selbach, Sverre M.

2017-06-01

The local and average structure of solid solutions of the multiferroic perovskite BiFeO 3 is investigated by synchrotron X-ray diffraction (XRD) and electron density functional theory (DFT) calculations. The average experimental structure is determined by Rietveld refinement and the local structure by total scattering data analyzed in real space with the pair distribution function (PDF) method. With equal concentrations of La on the Bi site or Mn on the Fe site, La causes larger structural distortions than Mn. Structural models based on DFT relaxed geometry give an improved fit to experimental PDFs compared to models constrained by the space groupmore » symmetry. Berry phase calculations predict a higher ferroelectric polarization than the experimental literature values, reflecting that structural disorder is not captured in either average structure space group models or DFT calculations with artificial long range order imposed by periodic boundary conditions. Only by including point defects in a supercell, here Bi vacancies, can DFT calculations reproduce the literature results on the structure and ferroelectric polarization of Mn-substituted BiFeO 3. The combination of local and average structure sensitive experimental methods with DFT calculations is useful for illuminating the structure-property-composition relationships in complex functional oxides with local structural distortions.« less

Edge-Cracking Behavior of CoCrFeMnNi High-Entropy Alloy During Hot Rolling

NASA Astrophysics Data System (ADS)

Won, Jong Woo; Kang, Minju; Kwon, Heoun-Jun; Lim, Ka Ram; Seo, Seong Moon; Na, Young Sang

2018-05-01

This work investigated edge-cracking behavior of equiatomic CoCrFeMnNi high-entropy alloy during hot rolling at rolling temperatures 500 ≤ T R ≤ 1000 °C. Edge cracks did not form in the material rolled at 500 °C, but widened and deepened into the inside of plate as T R increased from 500 °C. Edge cracks were most severe in the material rolled at 1000 °C. Mn-Cr-O type non-metallic inclusion and oxidation were identified as major factors that caused edge cracking. The inclusions near edge region acted as preferential sites for crack formation. Connection between inclusion cracks and surface cracks induced edge cracking. Rolling at T R ≥ 600 °C generated distinct inclusion cracks whereas they were not serious at T R = 500 °C, so noticeable edge cracks formed at T R ≥ 600 °C. At T R = 1000 °C, significant oxidation occurred at the crack surface. This accelerated edge crack penetration by embrittling the crack tip, so severe edge cracking occurred at T R = 1000 °C.

Critical evaluation of sequential leaching procedures for the determination of Ni and Mn species in welding fumes.

PubMed

Berlinger, B; Náray, M; Sajó, I; Záray, G

2009-06-01

In this work, welding fume samples were collected in a welding plant, where corrosion-resistant steel and unalloyed structural steel were welded by gas metal arc welding (GMAW) and manual metal arc welding (MMAW) techniques. The welding fumes were sampled with a fixed-point sampling strategy applying Higgins-Dewell cyclones. The following solutions were used to dissolve the different species of Ni and Mn: ammonium citrate solution [1.7% (m/v) diammonium hydrogen citrate and 0.5% (m/v) citric acid monohydrate] for 'soluble' Ni, 50:1 methanol-bromine solution for metallic Ni, 0.01 M ammonium acetate for soluble Mn, 25% acetic acid for Mn(0) and Mn(2+) and 0.5% hydroxylammonium chloride in 25% acetic acid for Mn(3+) and Mn(4+). 'Insoluble' Ni and Mn contents of the samples were determined after microwave-assisted digestion with the mixture of concentrated (cc). HNO(3), cc. HCl and cc. HF. The sample solutions were analysed by inductively coupled plasma quadrupole mass spectrometry and inductively coupled plasma atomic emission spectrometry. The levels of total Ni and Mn measured in the workplace air were different because of significant differences of the fume generation rates and the distributions of the components in the welding fumes between the welding processes. For quality control of the leaching process, dissolution of the pure stoichiometric Mn and Ni compounds and their mixtures weighing was investigated using the optimized leaching conditions. The results showed the adequacy of the procedure for the pure metal compounds. Based on the extraction procedures, the predominant oxidation states of Ni and Mn proved to be very different depending on the welding techniques and type of the welded steels. The largest amount of Mn in GMAW fumes were found as insoluble Mn (46 and 35% in case of corrosion-resistant steel and unalloyed structural steel, respectively), while MMAW fumes contain mainly soluble Mn, Mn(0) and Mn(2+) (78%) and Mn(3+) and Mn(4+) (54%) in case of corrosion-resistant steel and unalloyed structural steel, respectively. According to the results of the leaching procedures, GMAW fumes are rich in oxidic Ni (79%), while Ni compounds in welding fumes generated during MMAW are mainly in easily soluble form (44%). The crystalline phases were identified in each welding fume by X-ray powder diffraction (XRPD) technique as well. From the XRPD spectra, it is clear that GMAW fumes contain predominantly magnetite (FeFe(2)O(4)). In case of structural steel welding, there was a little amount of ferrite (alpha-Fe) also found. Welding fume generated during MMAW of structural steel contained a complex alkali-alkali earth fluoride phase (KCaF(3)-CaF(2)) and some magnetite and jakobsite (MnFe(2)O(4)). The XRPD results did not fully confirm the ones obtained from the extraction experiments. However, some results, for example the rate of soluble Ni and Mn compounds compared to the total, can be useful for further investigations of welding fumes.

Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

PubMed

Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

2015-11-01

Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential for rapid (re)formation of dissolved Cr(vi) above regulatory levels.

Arctic Deep Water Ferromanganese-Oxide Deposits Reflect the Unique Characteristics of the Arctic Ocean

NASA Astrophysics Data System (ADS)

Hein, James R.; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe J.; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah R.; Till, Claire P.

2017-11-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, and HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ˜15 Myr ago.

Arctic deep-water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

USGS Publications Warehouse

Hein, James; Konstantinova, Natalia; Mikesell, Mariah; Mizell, Kira; Fitzsimmons, Jessica N.; Lam, Phoebe; Jensen, Laramie T.; Xiang, Yang; Gartman, Amy; Cherkashov, Georgy; Hutchinson, Deborah; Till, Claire P.

2017-01-01

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits.The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.

Hydrothermal synthesis of cathode materials

NASA Astrophysics Data System (ADS)

Chen, Jiajun; Wang, Shijun; Whittingham, M. Stanley

A number of cathodes are being considered for the next generation of lithium ion batteries to replace the expensive LiCoO 2 presently used. Besides the layered oxides, such as LiNi yMn yCo 1-2 yO 2, a leading candidate is lithium iron phosphate with the olivine structure. Although this material is inherently low cost, a manufacturing process that produces electrochemically active LiFePO 4 at a low cost is also required. Hydrothermal reactions are one such possibility. A number of pure phosphates have been prepared using this technique, including LiFePO 4, LiMnPO 4 and LiCoPO 4; this method has also successfully produced mixed metal phosphates, such as LiFe 0.33Mn 0.33Co 0.33PO 4. Ascorbic acid was found to be better than hydrazine or sugar at preventing the formation of ferric ions in aqueous media. When conductive carbons are added to the reaction medium excellent electrochemical behavior is observed.

Electricity generation coupled with wastewater treatment using a microbial fuel cell composed of a modified cathode with a ceramic membrane and cellulose acetate film.

PubMed

Seo, Ha Na; Lee, Woo Jin; Hwang, Tae Sik; Park, Doo Hyun

2009-09-01

A noncompartmented microbial fuel cell (NCMFC) composed of a Mn(IV)-carbon plate and a Fe(III)-carbon plate was used for electricity generation from organic wastewater without consumption of external energy. The Fe(III)-carbon plate, coated with a porous ceramic membrane and a semipermeable cellulose acetate film, was used as a cathode, which substituted for the catholyte and cathode. The Mn(IV)-carbon plate was used as an anode without a membrane or film coating. A solar cell connected to the NCMFC activated electricity generation and bacterial consumption of organic matter contained in the wastewater. More than 99 degrees of the organic matter was biochemically oxidized during wastewater flow through the four NCMFC units. A predominant bacterium isolated from the anode surface in both the conventional and the solar cell-linked NCMFC was found to be more than 99 degrees similar to a Mn(II)-oxidizing bacterium and Burkeholderia sp., based on 16S rDNA sequence analysis. The isolate reacted electrochemically with the Mn(IV)-modified anode and produced electricity in the NCMFC. After 90 days of incubation, a bacterial species that was enriched on the Mn(IV)-modified anode surface in all of the NCMFC units was found to be very similar to the initially isolated predominant species by comparing 16S rDNA sequences.

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor

PubMed Central

Rusi; Chan, P. Y.; Majid, S. R.

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm-2. The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg-1 at current density of 1.85 Ag-1 in 0.5M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5M KOH and 0.5M KOH/0.04M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 103 Fg-1 and an energy density of 309 Whkg-1 in a 0.5MKOH/0.04MK3Fe(CN) 6 electrolyte at a current density of 10 Ag-1. The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications. PMID:26158447

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor.

PubMed

Rusi; Chan, P Y; Majid, S R

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm(-2). The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg(-1) at current density of 1.85 Ag(-1) in 0.5 M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5 M KOH and 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 10(3) Fg(-1) and an energy density of 309 Whkg(-1) in a 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolyte at a current density of 10 Ag(-1). The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications.

Creation of Technosols to decrease metal availability in pyritic tailings with addition of biochar and marble waste

NASA Astrophysics Data System (ADS)

Moreno-Barriga, Fabián; Acosta, José A.; Ángeles Muñoz, María; Faz, Ángel; Zornoza, Raúl

2017-04-01

Creation of Technosols with the use of different materials is a sustainable strategy to reclaim mine tailings and reduce metal mobility. For this purpose, a short-term incubation experiment was designed with biochars derived from pig manure (PM), crop residues (CR) and municipal solid waste (MSW) added to tailings alone or in combination with marble waste (MaW). We aimed to assess the efficiency of the different amendments to decrease Cd, Pb and Zn availability in the Technosols and the fractions where metals were retained. Results showed that all amendments reduced metal mobility, directly related to increases in pH. Those materials with higher content of carbonates were more effective to immobilize metals ( 99%). MSW was highly effective to decrease metal mobility owing to the higher carbonate content, but addition of MaW was needed to enhance metal immobilization with PM and CR. Decreases in Cd mobility were related to retention by the carbonate, Mn/Fe oxides and oxidizable (organic compounds) fractions. Decreases in Pb mobility were related to retention in the Mn/Fe oxides and residual fractions, while decreases in Zn mobility were related to retention in Mn/Fe oxides and oxidizable fractions. The increase in the retention of metals in all fractions was directly associated to increases in pH. Association of Zn and Pb with the oxidizable fraction was also related to the recalcitrance of the organic compounds, and so dependent on biochar type. SEM/EDX showed that biochar showed great affinity to interact with iron oxides, calcium sulfates and phyllosilicates. Acknowledgements This work was supported by Fundación Séneca (Agency of Science and Technology of the Region of Murcia, Spain) [grant number 18920/JLI/13].

Protective effect of Mn(III)-desferrioxamine B upon oxidative stress caused by ozone and acid rain in the Brazilian soybean cultivar Glycine max "Sambaiba".

PubMed

Esposito, Jéssica Bordotti Nobre; Esposito, Breno Pannia; Azevedo, Ricardo Antunes; Cruz, Luciano Soares; da Silva, Luzimar Campos; de Souza, Silvia Ribeiro

2015-04-01

This study aimed to investigate the effects of the Mn complex (Mn(III)-desferrioxamine B (MnDFB)) on oxidative stress in the Brazilian soybean cultivar Glycine max "Sambaiba" following exposure to ozone and acid rain. We determined the suitable dose of MnDFB to apply to G. max seedlings using a dose-response curve. The highest superoxide dismutase (SOD) activity and Mn content in leaves were found upon the application of 8 μM MnDFB. Thus, G. max seedlings pretreated with 8 μM MnDFB were individually exposed to ozone and acid rain simulated. Pretreatment with MnDFB reduced lipid peroxidation upon ozone exposure and increased SOD activity in leaves; it did not alter the metal content in any part of the plant. Conversely, following acid rain exposure, neither the metal content in leaves nor SOD enzyme activity were directly affected by MnDFB, unlike pH. Our findings demonstrated that exogenous MnDFB application before ozone exposure may modulate the MnSOD, Cu/ZnSOD, and FeSOD activities to combat the ROS excess in the cell. Here, we demonstrated that the applied dose of MnDFB enhances antioxidative defenses in soybean following exposure to acid rain and especially to ozone.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549

PM2.5 water-soluble elements in the southeastern United States: automated analytical method development, spatiotemporal distributions, source apportionment, and implications for heath studies

NASA Astrophysics Data System (ADS)

Fang, T.; Guo, H.; Verma, V.; Peltier, R. E.; Weber, R. J.

2015-06-01

Water-soluble redox-active metals are potentially toxic due to the ability to catalytically generate reactive oxygen species (ROS) in vivo, leading to oxidative stress. As part of the Southeastern Center for Air Pollution and Epidemiology (SCAPE), we developed a method to quantify water-soluble elements, including redox-active metals, from a large number of filter samples (N = 530) in support of the Center's health studies. PM2.5 samples were collected during 2012-2013 at various sites (three urban, two rural, a near-road, and a road-side site) in the southeastern US, using high-volume samplers. Water-soluble elements (S, K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Br, Sr, Ba, and Pb) were determined by extracting filters in deionized water and re-aerosolized for analyses by X-ray fluorescence (XRF) using an online aerosol element analyzer (Xact, Cooper Environmental). Concentrations ranged from detection limits (nominally 0.1 to 30 ng m-3) to 1.2 μg m-3, with S as the most abundant element, followed by Ca, K, Fe, Cu, Zn, and Ba. Positive Matrix Factorization (PMF) identified four factors that were associated with specific sources based on relative loadings of various tracers. These include: brake/tire wear (with tracers Ba and Cu); biomass burning (K); secondary formation (S, Se, and WSOC); and mineral dust (Ca). Of the four potentially toxic and relatively abundant metals (redox active Cu, Mn, Fe, and redox-inactive Zn), 51 % of Cu, 32 % of Fe, 17 % of Mn, and 45 % of Zn, were associated with the brake/tire factor. Mn was mostly associated with the mineral dust factor (45 %). These two factors were higher in warm (dryer) periods that favored particle re-suspension. Zn was found in a mixture of factors, with 26 % associated with mineral dust, 14 % biomass burning, and 13 % secondary formation. Roughly 50 % of Fe and 40 % of Cu was apportioned to the secondary formation factor, likely through increased solubility by sulfur-driven aerosol acidity. Linkages between sulfate and water-soluble Fe and Cu may account for some of the past observed associations between sulfate/sulfur oxide and health outcomes. For Cu, Mn, Fe, and Zn, only Fe was correlated with PM2.5 mass (r = 0.73-0.80). Overall, mobile source emissions generated through mechanical processes (re-entrained road dust, tire and break wear) and processing by secondary sulfate were major contributors to water-soluble metals known to be capable of generating ROS.

Structural Basis for Assembly of the MnIV/FeIII Cofactor in the Class Ic Ribonucleotide Reductase from Chlamydia trachomatis‡

PubMed Central

Dassama, Laura M.K.; Krebs, Carsten; Bollinger, J. Martin; Rosenzweig, Amy C.; Boal, Amie K.

2013-01-01

The class Ic ribonucleotide reductase (RNR) from Chlamydia trachomatis (Ct) employs a MnIV/FeIII cofactor in each monomer of its β2 subunit to initiate nucleotide reduction. The cofactor forms by reaction of MnII/FeII-β2 with O2. Previously, in vitro cofactor assembly from apo β2 and divalent metal ions produced a mixture of two forms, with Mn in site 1 (MnIV/FeIII) or site 2 (FeIII/MnIV), of which the more active MnIV/FeIII product predominates. Here we have addressed the basis for metal site-selectivity by solving X-ray crystal structures of apo, MnII, and MnII/FeII complexes of Ct β2. A structure obtained anaerobically with equimolar MnII, FeII, and apo protein reveals exclusive incorporation of MnII in site 1 and FeII in site 2, in contrast to the more modest site-selectivity achieved previously. Site-specificity is controlled thermodynamically by the apo protein structure, as only minor adjustments of ligands occur upon metal binding. Additional structures imply that, by itself, MnII binds in either site. Together the structures are consistent with a model for in vitro cofactor assembly in which FeII specificity for site 2 drives assembly of the appropriately configured heterobimetallic center, provided that FeII is substoichiometric. This model suggests that use of an MnIV/FeIII cofactor in vivo could be an adaptation to FeII limitation. A 1.8 Å resolution model of the MnII/FeII-β2 complex reveals additional structural determinants for activation of the cofactor, including a proposed site for side-on (η2) addition of O2 to FeII and a short (3.2 Å) MnII-FeII interionic distance, promoting formation of the MnIV/FeIV activation intermediate. PMID:23924396

Martensitic Transformations and Mechanical and Corrosion Properties of Fe-Mn-Si Alloys for Biodegradable Medical Implants

NASA Astrophysics Data System (ADS)

Drevet, Richard; Zhukova, Yulia; Malikova, Polina; Dubinskiy, Sergey; Korotitskiy, Andrey; Pustov, Yury; Prokoshkin, Sergey

2018-03-01

The Fe-Mn-Si alloys are promising materials for biodegradable metallic implants for temporary healing process in the human body. In this study, three different compositions are considered (Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si, all in wt pct). The phase composition analysis by XRD reveals ɛ-martensite, α-martensite, and γ-austenite in various proportions depending on the manganese amount. The DSC study shows that the starting temperature of the martensitic transformation ( M s) of the alloys decreases when the manganese content increases (416 K, 401 K, and 323 K (143 °C, 128 °C, and 50 °C) for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively). Moreover, mechanical compression tests indicate that these alloys have a much lower Young's modulus ( E) than pure iron (220 GPa), i.e., 145, 133, and 118 GPa for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively. The corrosion behavior of the alloys is studied in Hank's solution at 310 K (37 °C) using electrochemical experiments and weight loss measurements. The corrosion kinetics of the Fe-Mn-Si increases with the manganese content (0.48, 0.59, and 0.80 mm/year for the Fe23Mn5Si, Fe26Mn5Si, and Fe30Mn5Si alloys, respectively). The alloy with the highest manganese content shows the most promising properties for biomedical applications as a biodegradable and biomechanically compatible implant material.

Mn-oxidizing Bacteria in Oak Ridge, TN and the Potential for Mercury Remediation

NASA Astrophysics Data System (ADS)

Wright, K. L.; McNeal, K. S.; Han, F. X.

2012-12-01

East Fork Poplar Creek (EFPC) in Oak Ridge, TN was highly contaminated with elemental mercury in the 1950 and 1960. The area is still experiencing the effects of mercury contamination, and researchers are searching for ways to remediate the EFPC. One possible mechanism for bioremediation is the use of biogenic Mn oxides to remove heavy metals from water systems. Six native Pseudomonas bacteria species were isolated from the EFPC in order to examine biogenic Mn oxides production and bioremediation of Oak Ridge slurries. To investigate the biochemical interactions of Pseudomonas and the native microbial communities with Hg, Mn, Fe, S, six different slurry treatment groups were compared using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and cold vapor atomic absorption spectrometry (CVAAS). Oak Ridge slurries were autoclaved to inhibit microbial growth (group 1), autoclaved and amended with HgS (group 2), autoclaved and amended with Pseudomonas isolates and additional HgS (group 3), untreated slurry (group 4), normal slurry amended with HgS (group 5), and normal slurry amended with Pseudomonas isolates and additional HgS (group 6). The comparison of the autoclaved groups with the counterpart untreated and normal Oak Ridge slurries highlighted important microbial interactions. Also, the Pseudomonas isolates were grown separately in a MnSO4 media, and the individual bacteria were monitored for Mn-oxidization using ICP-AES and transmission electron microscopy (TEM). In the slurry sediments, the Pseudomonas isolates did produce Mn oxides which bound to mercury, and mercury bound to organic matter significantly decreased. However, after a significant decrease of dissolved mercury in the water, dissolved mercury was cycled back into the water system on day 10 of the study. Additionally, two individual native Oak Ridge Pseudomonas isolates demonstrated Mn-oxidization. Biogenic Mn oxides have the potential to decrease mercury cycling, however there is need for more in depth and long-term studies to confirm their sustained use as Hg bioremediators.

Complex, Precision Cast Columbium Alloy Gas Turbine Engine Nozzles Coated to Resist Oxidation.

DTIC Science & Technology

1980-04-01

Microstructures of Sprayed Specimens 64 Table 19 NS-4 Coated C129Y Alloy Specimens Weight Bisque Weight Sintered Weight Silicided Weight Pre-Oxidized...choice of another alloy , while perhaps assisting in the foundry process , would not have yielded a mechanical property data base with advantage over...Mo 250 ppm max; Fe 30 ppm max; Al , Ca, C, Si, Cr, Ni, Cu , Mn, Mg and Sn 10 ppm max each). Molybdenum វim powder (02 2000 ppm max; W 250 ppm max; Fe

Evaluation of air sparging and vadose zone aeration for remediation of iron and manganese-impacted groundwater at a closed municipal landfill.

PubMed

Pleasant, Saraya; O'Donnell, Amanda; Powell, Jon; Jain, Pradeep; Townsend, Timothy

2014-07-01

High concentrations of iron (Fe(II)) and manganese (Mn(II)) reductively dissolved from soil minerals have been detected in groundwater monitoring wells near many municipal solid waste landfills. Air sparging and vadose zone aeration (VZA) were evaluated as remedial approaches at a closed, unlined municipal solid waste landfill in Florida, USA. The goal of aeration was to oxidize Fe and Mn to their respective immobile forms. VZA and shallow air sparging using a partially submerged well screen were employed with limited success (Phase 1); decreases in dissolved iron were observed in three of nine monitoring wells during shallow air sparging and in two of 17 wells at VZA locations. During Phase 2, where deeper air sparging was employed, dissolved iron levels decreased in a significantly greater number of monitoring wells surrounding injection points, however no radial pattern was observed. Additionally, in wells affected positively by air sparging (mean total iron (FeTOT) <4.2mg/L, after commencement of air sparging), rising manganese concentrations were observed, indicating that the redox potential of the groundwater moved from an iron-reducing to a manganese-reducing environment. The mean FeTOT concentration observed in affected monitoring wells throughout the study was 1.40 mg/L compared to a background of 15.38 mg/L, while the mean Mn concentration was 0.60 mg/L compared to a background level of 0.27 mg/L. Reference wells located beyond the influence of air sparging areas showed little variation in FeTOT and Mn, indicating the observed effects were the result of air injection activities at study locations and not a natural phenomenon. Air sparging was found effective in intercepting plumes of dissolved Fe surrounding municipal landfills, but the effect on dissolved Mn was contrary to the desired outcome of decreased Mn groundwater concentrations. Copyright © 2014 Elsevier B.V. All rights reserved.

Heavy metal distributions in Peru Basin surface sediments in relation to historic, present and disturbed redox environments

NASA Astrophysics Data System (ADS)

Koschinsky, Andrea

Heavy metal distributions in deep-sea surface sediments and pore water profiles from five areas in the Peru Basin were investigated with respect to the redox environment and diagenetic processes in these areas. The 10-20-cm-thick Mn oxide-rich and minor metal-rich top layer is underlain by an increase in dissolved Mn and Ni concentrations resulting from the reduction of the MnO 2 phase below the oxic zone. The mobilised associated metals like Co, Zn and Cu are partly immobilised by sorption on clay, organic or Fe compounds in the post-oxic environment. Enrichment of dissolved Cu, Zn, Ni, Co, Pb, Cd, Fe and V within the upper 1-5 cm of the oxic zone can be attributed to the degradation of organic matter. In a core from one area at around 22-25 cm depth, striking enrichments of these metals in dissolved and solid forms were observed. Offset distributions between oxygen penetration and Mn reduction and the thickness of the Mn oxide-rich layer indicate fluctuations of the Mn redox boundary on a short-term time scale. Within the objectives of the German ATESEPP research programme, the effect of an industrial impact such as manganese nodule mining on the heavy metal cycle in the surface sediment was considered. If the oxic surface were to be removed or disturbed, oxygen would penetrate deep into the formerly suboxic sediment and precipitate Mn 2+ and metals like Ni and Co which are preferably scavenged by MnO 2. The solid enrichments of Cd, V, and other metals formed in post-oxic environments would move downward with the new redox boundary until a new equilibrium between oxygen diffusion and consumption is reached.

Tuning the magnetism of ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Viñas, S. Liébana; Simeonidis, K.; Li, Z.-A.; Ma, Z.; Myrovali, E.; Makridis, A.; Sakellari, D.; Angelakeris, M.; Wiedwald, U.; Spasova, M.; Farle, M.

2016-10-01

The importance of magnetic interactions within an individual nanoparticle or between adjacent ones is crucial not only for the macroscopic collective magnetic behavior but for the AC magnetic heating efficiency as well. On this concept, single-(MFe2O4 where M=Fe, Co, Mn) and core-shell ferrite nanoparticles consisting of a magnetically softer (MnFe2O4) or magnetically harder (CoFe2O4) core and a magnetite (Fe3O4) shell with an overall size in the 10 nm range were synthesized and studied for their magnetic particle hyperthermia efficiency. Magnetic measurements indicate that the coating of the hard magnetic phase (CoFe2O4) by Fe3O4 provides a significant enhancement of hysteresis losses over the corresponding single-phase counterpart response, and thus results in a multiplication of the magnetic hyperthermia efficiency opening a novel pathway for high-performance, magnetic hyperthermia agents. At the same time, the existence of a biocompatible Fe3O4 outer shell, toxicologically renders these systems similar to iron-oxide ones with significantly milder side-effects.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

PubMed

Hong, Yong Seok; Kinney, Kerry A; Reible, Danny D

2011-03-01

Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase. Copyright © 2010 SETAC.

MN Carbonates in the Martian Meteorite Nakhla: Possible Evidence of Brine Evaporation

NASA Technical Reports Server (NTRS)

Bailey, J. V.; McKay, D. S.; Wentworth, S. J.

2003-01-01

The importance of secondary phases in martian meteorites lies in their potential to provide clues about the martian environments responsible for their formation. During this study, we analyzed a number of carbonate-bearing fracture surfaces from the Nakhla meteorite. Here we describe the physical and chemical properties of several manganese-calcium-rich siderites. Additionally, we describe a potential model for the formation and alteration of these carbonates, and we suggest constraints on the conditions responsible for their precipitation. Nakhla is an olivine-bearing clinopyroxenite with minor amounts of feldspar, FeS, and Fe oxides. Secondary mineral assemblages include vein filling clay with embedded iron oxides, a calcium sulfate, amorphous silica, chlorapatite, halite and carbonates. Bridges and Grady suggested that the carbonates in Nakhla formed from brine evaporation. Isotope studies of the Mn rich siderite are also consistent with formation from hydrothermal fluids with an upper T constraint of 170 C.

Mineralogical characteristics of Mn coatings from different weathering environments in China: clues on their formation

NASA Astrophysics Data System (ADS)

Xu, Xiaoming; Ding, Hongrui; Li, Yan; Lu, Anhuai; Li, Yan; Wang, Changqiu

2018-03-01

Identification of Mn oxides in natural Mn coatings is very difficult due to their poor crystallinity, fine grains, complex chemistry and tiny amounts. In this work, we investigated three types of Mn coatings including rock varnish, dendrite and soil Fe-Mn cutan from different weathering environments in China. Optical microscope, scanning electron microscope, energy dispersive X-ray spectroscopy and micro-Raman spectrometer were employed to achieve non-destructive, sensitive, in-situ and micro analysis on their mineral assemblages, micromorphological features and elemental distribution characteristics. The observed results suggest that rock varnish and soil cutan comprise birnessite, while dendrite is mainly composed of hollandite. Rock varnish with a layered structure has a clear boundary with its substrate, and microlaminations which arise from the fluctuations in Mn content (6.42-17.07 wt%) within the sample profile are obvious on closer inspection. Branch-like dendrite is rich in Mn (32.53-42.96 wt%) but poor in Si and Al, which shows a pilotaxitic texture with its substrate. Soil Fe-Mn cutan can be further divided into an outer black Mn-rich (8.26-13.58 wt%) belt and an inner yellowish-brown Fe-rich (2.06-4.85 wt%) belt, and a clear border can be identified between these two belts. Mn in the substrate of rock varnish and soil cutan is below detection limit while it can be detected in the substrate of dendrite (1.43-7.83 wt%). Our in-situ analysis provides more precise results than traditional powder test. These mineralogical characteristics indicate that dendrite is most likely endogenic, while rock varnish and soil cutan are external accretion formed under different weathering environments.

Ferromagnetic resonance investigation in as-prepared NiFe/FeMn/NiFe trilayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, S. J.; Xu, K.; Yu, L. M.

2007-06-01

NiFe/FeMn/NiFe trilayer prepared by dc magnetron sputtering was systematically investigated by ferromagnetic resonance technique (FMR) at room temperature. For NiFe/FeMn/NiFe trilayer, there are two distinct resonance peaks both in in-plane and out-of-plane FMR spectra, which are attributed to the two NiFe layers, respectively. The isotropic in-plane resonance field shift is negative for the bottom NiFe layer, while positive for the top NiFe layer. And, such phenomena result from the negative interfacial perpendicular anisotropy at the bottom NiFe/FeMn interface and positive interfacial perpendicular anisotropy at the top FeMn/NiFe interface. The linewidth of the bottom NiFe layer is larger than that ofmore » the top NiFe layer, which might be related to the greater exchange coupling at the bottom NiFe/FeMn interface.« less

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

USGS Publications Warehouse

White, A.F.; Peterson, M.L.

1996-01-01

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

Reduction of aqueous transition metal species on the surfaces of Fe(II) -containing oxides

NASA Astrophysics Data System (ADS)

White, Art F.; Peterson, Maria L.

1996-10-01

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25°C. For an aqueous transition metal m, such reactions are 3[FeFe23+]O+2/nm→4[Fe23+]O+Fe+2/nm and 3[FeTi]O+→Fe23+TiO+Fe+2/nm, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] → [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe 2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 × 10 -10 mol m -2 s -1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe 2+ is oxidized homogeneously in solution to Fe 3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

Binder-jetting 3D printing and alloy development of new biodegradable Fe-Mn-Ca/Mg alloys.

PubMed

Hong, Daeho; Chou, Da-Tren; Velikokhatnyi, Oleg I; Roy, Abhijit; Lee, Boeun; Swink, Isaac; Issaev, Ilona; Kuhn, Howard A; Kumta, Prashant N

2016-11-01

3D printing of various biomaterials including titanium and stainless steel has been studied for treating patients with cranio-maxillofacial bone defect. The potential long term complications with use of inert biometals have opened the opportunities for use of biodegradable metals in the clinical arena. The authors previously reported that binder-jet 3D printing technique enhanced the degradation rates of biodegradable Fe-Mn alloy by creating engineered micropores rendering the system attractive as biodegradable implantable devices. In the present study, the authors employed CALPHAD modeling to systematically study and modify the Fe-Mn alloy composition to achieve enhanced degradation rates. Accordingly, Ca and Mg addition to Fe-35wt% Mn solid solution predicted increase in degradation rates. In order to validate the CALPHAD results, Fe - (35-y)wt% Mn - ywt% X (X=Ca, Mg, and y=0, 1, 2) were synthesized by using high energy mechanical alloying (HEMA). Sintered pellets of Fe-Mn-Ca and Fe-Mn-Mg were then subjected to potentiodynamic polarization (PDP) and live/dead cell viability tests. Sintered pellets of Fe-Mn, Fe-Mn-Ca, and Fe-Mn-Mg also exhibited MC3T3 murine pre-osteoblast cells viability in the live/dead assay results. Fe-Mn and Fe-Mn-1Ca were thus accordingly selected for 3D printing and the results further confirmed enhanced degradation of Ca addition to 3D printed constructs validating the theoretical and alloy development studies. Live/dead and MTT cell viability results also confirmed good cytocompatibility of the 3D-printed Fe-Mn and Fe-Mn-1Ca constructs. Bone grafting is widely used for the treatment of cranio-maxillofacial bone injuries. 3D printing of biodegradable Fe alloy is anticipated to be advantageous over current bone grafting techniques. 3D printing offers the fabrication of precise and tailored bone grafts to fit the patient specific bone defect needs. Biodegradable Fe alloy is a good candidate for 3D printing synthetic grafts to regenerate bone tissue without eliciting complications. CALPHAD theoretical models were used to develop new Fe-Mn-Ca/Mg alloys to enhance the degradation rates of traditional Fe-Mn alloys. In vitro experimental results also showed enhanced degradation rates and good cytocompatibility of sintered Fe-Mn-Ca/Mg compacts. 3D printing of Fe-Mn and Fe-Mn-1Ca alloys further demonstrated their feasibility as potentially viable bone grafts for the future. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Genesis of a regionally widespread celadonitic chert ironstone bed overlying upper Lias manganese deposits, Hungary

USGS Publications Warehouse

Polgari, Marta; Hein, J.R.; Toth, M.; Brukner-Wein, A.; Vigh, T.; Biro, L.; Cserhati, C.

2010-01-01

Mineralogy and chemical composition are presented for a chert-ironstone bed that overlies the ??rk??t Mn deposit. This bed is mottled green-brown in its lower and upper parts, which are composed of quartz, goethite and celadonite. These parts of the bed are interpreted to be strongly altered tuffs, reflecting oxidic, low-temperature alteration of a hydrated, Fe-rich, Al-poor tuff, and K and Mg uptake from seawater. The middle part of the bed is a mineralized bacterial mat (quartz, goethite). Textures resembling bacterial cells and colonies are common, with wavy, bulbous laminations composed of mounds overlying a mesh-work stromatolite-like texture constructed of micrometre-size Fe oxides. This bed is concordant with the underlying Mn deposit and marks the termination of Mn accumulation. Although no genetic connection exists between the two, the rocks adjacent to the contact record the oceanographic and bottom-water conditions extant when accumulation of one of the major Mn deposits of Europe ended, when the Transdanubian Range was located in the middle of the Adria-Apulian microcontinent between the Neotethys and Atlantic-Ligurian seaways. A pyroclastic origin for part of the bed has significance for the Toarcian of Central Europe because evidence of volcanism occurring at that time is otherwise sparse. ?? 2010 Geological Society of London.

Molecular electrocatalysts for oxidation of hydrogen using earth-abundant metals: shoving protons around with proton relays.

PubMed

Bullock, R Morris; Helm, Monte L

2015-07-21

Sustainable, carbon-neutral energy is needed to supplant the worldwide reliance on fossil fuels in order to address the persistent problem of increasing emissions of CO2. Solar and wind energy are intermittent, highlighting the need to develop energy storage on a huge scale. Electrocatalysts provide a way to convert between electrical energy generated by renewable energy sources and chemical energy in the form of chemical bonds. Oxidation of hydrogen to give two electrons and two protons is carried out in fuel cells, but the typical catalyst is platinum, a precious metal of low earth abundance and high cost. In nature, hydrogenases based on iron or iron/nickel reversibly oxidize hydrogen with remarkable efficiencies and rates. Functional models of these enzymes have been synthesized with the goal of achieving electrocatalytic H2 oxidation using inexpensive, earth-abundant metals along with a key feature identified in the [FeFe]-hydrogenase: an amine base positioned near the metal. The diphosphine ligands P(R)2N(R')2 (1,5-diaza-3,7-diphosphacyclooctane with alkyl or aryl groups on the P and N atoms) are used as ligands in Ni, Fe, and Mn complexes. The pendant amines facilitate binding and heterolytic cleavage of H2, placing the hydride on the metal and the proton on the amine. The pendant amines also serve as proton relays, accelerating intramolecular and intermolecular proton transfers. Electrochemical oxidations and deprotonations by an exogeneous amine base lead to catalytic cycles for oxidation of H2 (1 atm) at room temperature for catalysts derived from [Ni(P(Cy)2N(R')2)2](2+), Cp(C6F5)Fe(P(tBu)2N(Bn)2)H, and MnH(P(Ph)2N(Bn)2)(bppm)(CO) [bppm = (PAr(F)2)2CH2]. In the oxidation of H2 catalyzed by [Ni(P(Cy)2N(R')2)2](2+), the initial product observed experimentally is a Ni(0) complex in which two of the pendant amines are protonated. Two different pathways can occur from this intermediate; deprotonation followed by oxidation occurs with a lower overpotential than the alternate pathway involving oxidation followed by deprotonation. The Mn cation [Mn(P(Ph)2N(Bn)2)(bppm)(CO)](+) mediates the rapid (>10(4) s(-1) at -95 °C), reversible heterolytic cleavage of H2. Obtaining the optimal benefit of pendant amines incorporated into the ligand requires that the pendant amine be properly positioned to interact with a M-H or M(H2) bond. In addition, ligands are ideally selected such that the hydride-acceptor ability of the metal and the basicity of a pendant are tuned to give low barriers for heterolytic cleavage of the H-H bond and subsequent proton transfer reactions. Using these principles allows the rational design of electrocatalysts for H2 oxidation using earth-abundant metals.

Magnetic interactions in BiFe0.5Mn0.5O3 films and BiFeO3/BiMnO3 superlattices

NASA Astrophysics Data System (ADS)

Xu, Qingyu; Sheng, Yan; Khalid, M.; Cao, Yanqiang; Wang, Yutian; Qiu, Xiangbiao; Zhang, Wen; He, Maocheng; Wang, Shuangbao; Zhou, Shengqiang; Li, Qi; Wu, Di; Zhai, Ya; Liu, Wenqing; Wang, Peng; Xu, Y. B.; Du, Jun

2015-03-01

The clear understanding of exchange interactions between magnetic ions in substituted BiFeO3 is the prerequisite for the comprehensive studies on magnetic properties. BiFe0.5Mn0.5O3 films and BiFeO3/BiMnO3 superlattices have been fabricated by pulsed laser deposition on (001) SrTiO3 substrates. Using piezoresponse force microscopy (PFM), the ferroelectricity at room temperature has been inferred from the observation of PFM hysteresis loops and electrical writing of ferroelectric domains for both samples. Spin glass behavior has been observed in both samples by temperature dependent magnetization curves and decay of thermo-remnant magnetization with time. The magnetic ordering has been studied by X-ray magnetic circular dichroism measurements, and Fe-O-Mn interaction has been confirmed to be antiferromagnetic (AF). The observed spin glass in BiFe0.5Mn0.5O3 films has been attributed to cluster spin glass due to Mn-rich ferromagnetic (FM) clusters in AF matrix, while spin glass in BiFeO3/BiMnO3 superlattices is due to competition between AF Fe-O-Fe, AF Fe-O-Mn and FM Mn-O-Mn interactions in the well ordered square lattice with two Fe ions in BiFeO3 layer and two Mn ions in BiMnO3 layer at interfaces.

Microstructural Characterization of Base Metal Alloys with Conductive Native Oxides for Electrical Contact Applications

NASA Astrophysics Data System (ADS)

Senturk, Bilge Seda

Metallic contacts are a ubiquitous method of connecting electrical and electronic components/systems. These contacts are usually fabricated from base metals because they are inexpensive, have high bulk electrical conductivities and exhibit excellent formability. Unfortunately, such base metals oxidize in air under ambient conditions, and the characteristics of the native oxide scales leads to contact resistances orders of magnitude higher than those for mating bare metal surface. This is a critical technological issue since the development of unacceptably high contact resistances over time is now by far the most common cause of failure in electrical/electronic devices and systems. To overcome these problems, several distinct approaches are developed for alloying base metals to promote the formation of self-healing inherently conductive native oxide scales. The objective of this dissertation study is to demonstrate the viability of these approaches through analyzing the data from Cu-9La (at%) and Fe-V binary alloy systems. The Cu-9 La alloy structure consists of eutectic colonies tens of microns in diameter wherein a rod-like Cu phase lies within a Cu6La matrix phase. The thin oxide scale formed on the Cu phase was found to be Cu2O as expected while the thicker oxide scale formed on the Cu6La phase was found to be a polycrystalline La-rich Cu2O. The enhanced electrical conductivity in the native oxide scale of the Cu-9La alloy arises from heavy n-type doping of the Cu2O lattice by La3+. The Fe-V alloy structures consist of a mixture of large elongated and equiaxed grains. A thin polycrystalline Fe3O4 oxide scale formed on all of the Fe-V alloys. The electrical conductivities of the oxide scales formed on the Fe-V alloys are higher than that formed on pure Fe. It is inferred that this enhanced conductivity arises from doping of the magnetite with V+4 which promotes electron-polaron hopping. Thus, it has been demonstrated that even in simple binary alloy systems one can obtain a dramatic reduction in the contact resistances of alloy oxidized surfaces as compared with those of the pure base metals.

A-site ordered quadruple perovskite oxides

NASA Astrophysics Data System (ADS)

Youwen, Long

2016-07-01

The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.

PubMed

Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G

2014-04-01

Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.

Analysis of the relationship between rusty root incidences and soil properties in Panax ginseng

NASA Astrophysics Data System (ADS)

Wang, Q. X.; Xu, C. L.; Sun, H.; Ma, L.; Li, L.; Zhang, D. D.; Zhang, Y. Y.

2016-08-01

Rusty root is a serious problem in ginseng cultivation that limits the production and quality of ginseng worldwide. The Changbai Mountains are the most famous area for ginseng cultivation in China. To clarify the relationship between rusty root and soil characteristics, physico-chemical properties and enzymatic activities of soil collected from five different fields in the Changbai Mountains were analyzed and a controlled experiment carried out by increasing the concentration of Fe (II). Soil bulk density, moisture, total iron (Fe) and total manganese (Mn) concentrations and polyphenol oxidase (PPO) activity were significantly higher in rusty root than healthy root groups (two-sample test, P<0.05 or P<0.01), respectively. Pearson test showed that there was a significant positive correlation between rusty root index and pH, N, Fe, Mn, Al, Zn and Ca of soil samples collected from fields (P<0.05 or P<0.01), and a significant positive correlation also occurred between rusty root index and Fe (II) added to soil in Fe (II) inducing rusty root (P<0.01). Physiological factors may be very important roles giving rise to ginseng rusty root. Fe (III) reduction and Fe (II) oxidation could be important in increasing the incidence of rusty root. Soil moisture and bulk density of non-rhizosphere soil not attached to the root surface, and pH, N and PPO content of rhizosphere soils attached to the root surface were heavily involved in the reduction, oxidation and sequestration of metal ions.

Hot gas, regenerative, supported H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Voecks, Gerald E. (Inventor); Sharma, Pramod K. (Inventor)

1993-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from moderately high temperature (usually 200.degree. C.-550.degree.C.) gas streams comprise a porous, high surface area aluminosilicate support, suitably a zeolite, and most preferably a sodium deficient zeolite containing 1 to 20 weight percent of binary metal oxides. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O contained in the support. The sorbent effectively removes H.sub.2 S from the host gas stream in high efficiency and can be repetitively regenerated at least 10 times without loss of activity.

Oxidation of β-blockers by birnessite: Kinetics, mechanism and effect of metal ions.

PubMed

Chen, Yong; Lu, Xiye; Liu, Lu; Wan, Dong; Chen, Huabin; Zhou, Danna; Sharma, Virender K

2018-03-01

Manganese dioxides are ubiquitous in natural waters, soils, and sediments and play an important role in oxidative transformation of organic pollutants. This work presents the kinetics of the oxidation of selected β-blockers, betaxolol, metoprolol, and atenolol by birnessite (δ-MnO 2 ) as a function of concentration of the β-blocker, dosage of δ-MnO 2 , and solution pH. The values of pseudo-first-order rate constants (k obs ) of β-blockers decreased in the order betaxolol > atenolol > metoprolol, which was positively correlated with their acid dissociation constants (K a ). Effect of series of metal ions (Fe 3+ , Cr 3+ , Al 3+ , Pb 2+ , Cu 2+ , Zn 2+ , Ni 2+ , Cd 2+ , Mg 2+ , and Ca 2+ ) on the degradation of β-blockers by δ-MnO 2 was systematically examined. All of these metal ions inhibited the oxidation reaction under the same constant ionic strength. The inhibition efficiency was positively correlated with the logarithm of stability constant of metal ions in aqueous solution (logK MeOH ). By LC-ESI-MS/MS analyses, the oxidation of β-blockers primarily involved hydroxylation and cleavage of the parent molecules to the short branched chain compounds. An electron transfer mechanism for the oxidation of β-blockers by δ-MnO 2 was proposed. The oxidation was initiated by the electron transfer from the nonbonding electrons on nitrogen (N-electrons) of β-blockers to δ-MnO 2 , followed by transformation of radical intermediates. These findings will help to understand the oxidation processes of β-blockers and predict the effect of metal ions on the removal of pollutants by δ-MnO 2 in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the Vistula River plume (southern Baltic Sea).

PubMed

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.

Welding fumes from stainless steel gas metal arc processes contain multiple manganese chemical species.

PubMed

Keane, Michael; Stone, Samuel; Chen, Bean

2010-05-01

Fumes from a group of gas metal arc welding (GMAW) processes used on stainless steel were generated using three different metal transfer modes and four different shield gases. The objective was to identify and measure manganese (Mn) species in the fumes, and identify processes that are minimal generators of Mn species. The robotic welding system was operated in short-circuit (SC) mode (Ar/CO2 and He/Ar), axial spray (AXS) mode (Ar/O2 and Ar/CO2), and pulsed axial-spray (PAXS) mode (Ar/O2). The fumes were analyzed for Mn by a sequential extraction process followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis, and by X-ray diffraction (XRD). Total elemental Mn, iron (Fe), chromium (Cr) and nickel (Ni) were separately measured after aqua regia digestion and ICP-AES analysis. Soluble Mn2+, Fe2+, Fe3+, and Ni2+ in a simple biological buffer (phosphate-buffered saline) were determined at pH 7.2 and 5.0 after 2 h incubation at 37 C by ion chromatography. Results indicate that Mn was present in soluble form, acid-soluble form, and acid-soluble form after reduction by hydroxylamine, which represents soluble Mn0 and Mn2+ compounds, other Mn2+ compounds, and (Mn3+ and Mn4+) compounds, respectively. The dominant fraction was the acid-soluble Mn2+ fraction, but results varied with the process and shield gas. Soluble Mn mass percent in the fume ranged from 0.2 to 0.9%, acid-soluble Mn2+ compounds ranged from 2.6 to 9.3%, and acid plus reducing agent-soluble (Mn3+ and Mn4+) compounds ranged from 0.6 to 5.1%. Total Mn composition ranged from 7 to 15%. XRD results showed fumes had a crystalline content of 90-99% Fe3O4, and showed evidence of multiple Mn oxides, but overlaps and weak signals limited identification. Small amounts of the Mn2+ in the fume (<0.01 to ≈ 1% or <0.1 to ≈ 10 microg ml(-1)) and Ni2+ (<0.01 to ≈ 0.2% or <0.1 to ≈ 2 mg ml(-1)) ions were found in biological buffer media, but amounts were highly dependent on pH and the welding process. Mn generation rates for the fractions were tabulated, and the influence of ozone is discussed. The conclusions are that exposures to welding fumes include multiple Mn species, both soluble and insoluble, and that exposures to Mn species vary with specific processes and shield gases.

A novel sandwich Fe-Mn damping alloy with ferrite shell prepared by vacuum annealing

NASA Astrophysics Data System (ADS)

Qian, Bingnan; Peng, Huabei; Wen, Yuhua

2018-04-01

To improve the corrosion resistance of high strength Fe-Mn damping alloys, we fabricated a novel sandwich Fe-17.5Mn damping alloy with Mn-depleted ferrite shell by vacuum annealing at 1100 °C. The formation behavior of the ferrite shell obeys the parabolic law for the vacuum annealed Fe-17.5Mn alloy at 1100 °C. The sandwich Fe-17.5Mn alloy with ferrite shell exhibits not only better corrosion resistance but also higher damping capacity than the conventional annealed Fe-17.5Mn alloy under argon atmosphere. The existence of only ferrite shell on the surface accounts for the better corrosion in the sandwich Fe-17.5Mn alloy. The better damping capacity in the sandwich Fe-17.5Mn alloy is owed to more stacking faults inside both ɛ martensite and γ austenite induced by the stress from ferrite shell. Vacuum annealing is a new way to improve the corrosion resistance and damping capacity of Fe-Mn damping alloys.

Removal of ethylene from air stream by adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts supported on zeolite.

PubMed

Trinh, Quang Hung; Lee, Sang Baek; Mok, Young Sun

2015-03-21

Dynamic adsorption of ethylene on 13X zeolite-supported Ag and Ag-M(x)O(y) (M: Co, Cu, Mn, and Fe), and plasma-catalytic oxidation of the adsorbed ethylene were investigated. The experimental results showed that the incorporation of Ag into zeolite afforded a marked enhancement in the adsorptivity for ethylene. The addition of transition metal oxides was found to have a positive influence on the ethylene adsorption, except Fe(x)O(y). The presence of the additional metal oxides, however, appeared to somewhat interrupt the diffusion of ozone into the zeolite micro-pores, leading to a decrease in the plasma-catalytic oxidation efficiency of the ethylene adsorbed there. Among the second additional metal oxides, Fe(x)O(y) was able to reduce the emission of ozone during the plasma-catalytic oxidation stage while keeping a high effectiveness for the oxidative removal of the adsorbed ethylene. The periodical treatment consisting of adsorption followed by plasma-catalytic oxidation may be a promising energy-efficient ethylene abatement method. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

USGS Publications Warehouse

Huebner, J.S.; Flohr, M.J.K.; Grossman, J.N.

1992-01-01

Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and therefore were the protoliths that most effectively diluted the REE-rich background resulting from fine clastic material (derived from distal turbidites). The variation of the Ce anomaly and U/Th among diverse lithologies and the differences in Mn oxidation states are consistent with progressive dilution of reduced subsurface fluids with oxidized seawater. By this scheme, rhodochrosite, gageite and hausmannite were deposited from the most reduced fluids, braunite from intermediate mixtures, and Mn-silicates from the sub-seafloor fluids most diluted with fresh seawater. Comparison of the Buckeye with other lens-like and sheet-like deposits having high Mn/Fe and containing Mn3+ and/or Mn2+ suggests that each had three essential fluxes: a sub-seafloor source of Mn, a local source of very soluble silica and a source of relatively fresh, oxygenated water. Additional fluxes, such as clastics, appear to be more characteristic of the paleoenvironment than the three essential fluxes. ?? 1992.

Degradation kinetics and transformation products of chlorophene by aqueous permanganate.

PubMed

Xu, Xinxin; Chen, Jing; Wang, Siyuan; Ge, Jiali; Qu, Ruijuan; Feng, Mingbao; Sharma, Virender K; Wang, Zunyao

2018-07-01

This paper evaluates the oxidation of an antibacterial agent, chlorophene (4-chloro-2-(phenylmethyl)phenol, CP), by permanganate (Mn(VII)) in water. Second-order rate constant (k) for the reaction between Mn(VII) and CP was measured as (2.05 ± 0.05) × 10 1  M -1  s -1 at pH 7.0 for an initial CP concentration of 20.0 μM and Mn(VII) concentration of 60.0 μM. The value of k decreased with increasing pH in the pH range of 5.0-7.0, and then increased with an increase in solution pH from 7.0 to 10.0. The presence of MnO 2 and Fe 3+ in water generally enhanced the removal of CP, while the effect of humic acid was not obvious. Fourteen oxidation products of CP were identified by an electrospray time-of-flight mass spectrometer, and direct oxidation, ring-opening, and decarboxylation were mainly observed in the reaction process. The initial reaction sites of CP by Mn(VII) oxidation were rationalized by density functional theory calculations. Toxicity changes of the reaction solutions were assessed by the luminescent bacteria P. phosphoreum, and the intermediate products posed a relatively low ecological risk during the degradation process. The efficient removal of CP in secondary clarifier effluent and river water demonstrated the potential application of this Mn(VII) oxidation method in water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Decolorization of Methylene Blue by Persulfate Activated with FeO Magnetic Particles.

PubMed

Hung, Chang-Mao; Chen, Chiu-Wen; Liu, Yi-Yuan; Dong, Cheng-Di

2016-08-01

In this study, the degradation of methylene blue (MB) was conducted to evaluate the feasibility of using persulfate oxidation activated with iron oxide (FeO) magnetic particles. The results demonstrated that the decolorization rate of MB increased with increasing FeO concentration, exhibiting maximum efficiency at pH0 3.0. The kinetics of MB was studied in the binary FeO catalyst and persulfate oxidation system. The surface properties of FeO before and after reaction was analyzed using cyclic voltammogram (CV), three-dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy, zeta potential, particle size distribution measurements, X-ray diffraction (XRD) and environmental scanning electron microscopy-energy dispersive X-ray spectrometry (ESEM-EDS). The CV data indicated that a reversible redox reaction holds the key to explaining the significant activity of the catalyst. EEFM was used to evaluate the catalyst yield of FeO by fluorescence intensity plots with excitation/emission at 220/300 nm and 260/300 nm. The XRD and ESEM-EDS results confirmed the presence of FeO in the catalyst.

Comparison of methods for the removal of organic carbon and extraction of chromium, iron and manganese from an estuarine sediment standard and sediment from the Calcasieu River estuary, Louisiana, U.S.A.

USGS Publications Warehouse

Simon, N.S.; Hatcher, S.A.; Demas, C.

1992-01-01

U.S. National Bureau of Standards (NBS) estuarine sediment 1646 from the Chesapeake Bay, Maryland, and surface sediment collected at two sites in the Calcasieu River estuary, Louisiana, were used to evaluate the dilute hydrochloric acid extraction of Cr, Fe and Mn from air-dried and freeze-dried samples that had been treated by one of three methods to remove organic carbon. The three methods for the oxidation and removal of organic carbon were: (1) 30% hydrogen peroxide; (2) 30% hydrogen peroxide plus 0.25 mM pyrophosphate; and (3) plasma oxidation (low-temperature ashing). There was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the percent of organic carbon removed by the three methods. Generally, there was no statistically significant difference at the 95% confidence level between air- and freeze-dried samples with respect to the concentration of Cr, Fe and Mn that was extracted, regardless of the extraction technique that was used. Hydrogen peroxide plus pyrophosphate removed the most organic carbon from sediment collected at the site in the Calcasieu River that was upstream from industrial outfalls. Plasma oxidation removed the most organic carbon from the sediment collected at a site in the Calcasieu River close to industrial outfalls and from the NBS estuarine sediment sample. Plasma oxidation merits further study as a treatment for removal of organic carbon. Operational parameters can be chosen to limit the plasma oxidation of pyrite which, unlike other Fe species, will not be dissolved by dilute hydrochloric acid. Preservation of pyrite allows the positive identification of Fe present as pyrite in sediments. ?? 1992.

Soft x-ray absorption spectroscopy study of the electronic structures of the MnFe Prussian blue analogs (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] H2O

NASA Astrophysics Data System (ADS)

Lee, Eunsook; Seong, Seungho; Kim, Hyun Woo; Kim, D. H.; Thakur, Nidhi; Yusuf, S. M.; Kim, Bongjae; Min, B. I.; Kim, Younghak; Kim, J.-Y.; de Groot, F. M. F.; Kang, J.-S.

2017-11-01

The electronic structures of Prussian blue analog (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] cyanides have been investigated by employing soft x-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) at the Fe and Mn L (2 p ) edges. The measured XAS spectra have been analyzed with the configuration-interaction (CI) cluster model calculations. The valence states of the Fe and Mn ions are found to be Fe2 +-Fe3 + mixed valent, with an average valency of v (Fe )˜2.8 and nearly divalent (Mn2 +), respectively. Our Mn/Fe 2 p XMCD study supports that Mn2 + ions are in the high-spin states while Fe2 +-Fe3 + ions are in the low-spin states. The Fe and Mn 2 p XAS spectra are found to be essentially the same for 80 ≤T ≤ 300 K, suggesting that a simple charge transfer upon cooling from Fe3 +-CN -Mn2 + to Fe2 +-CN -Mn3 + does not occur in (RbxBay) Mn[3 -(x +2 y )]/2[Fe (CN) 6] . According to the CI cluster model analysis, it is necessary to take into account both the ligand-to-metal charge transfer and the metal-to-ligand charge transfer in describing Fe 2 p XAS, while the effect of charge transfer is negligible in describing Mn 2 p XAS. The CI cluster model analysis also shows that the trivalent Fe3 + ions have a strong covalent bonding with the C ≡N ligands and are under a large crystal-field energy of 10 D q ˜3 eV, in contrast to the weak covalency effect and a small 10 D q ˜0.6 eV for the divalent Mn2 + ions.

Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling.

PubMed

Morrison, Stan J; Metzler, Donald R; Dwyer, Brian P

2002-05-01

Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

The Mn-Fe negative correlation in olivines in ALHA 77257 ureilite

NASA Technical Reports Server (NTRS)

Miyamoto, M.; Furuta, T.; Fujii, N.; Mckay, D. S.; Lofgren, G. E.; Duke, M. B.

1993-01-01

An electron probe microanalyzer is used to measure the Mn, Fe, and oxygen zoning profiles of olivines in the ALHA 77257 ureilite. This is done to study the effects of reduction on the Mn-Fe value, as ureilite olivines exhibit thin reduced rims. Since the Mn content gradually increases toward the rim of ureilite olivines, while the Fa (= 100 x Fe/(Mg + Fe), mol percent) component decreases, the Mn-Fe content of olivine is likely related to redox conditions. The results of melting experiments suggest that the Mn-Fe positive correlation is related to temperature and that the negative correlation of Mn-Fe in olivine and low-Ca pyroxene is related to reduction.

Trace metals partitioning between particulate and dissolved phases along a tropical mangrove estuary (Can Gio, Vietnam).

PubMed

Thanh-Nho, Nguyen; Strady, Emilie; Nhu-Trang, Tran-Thi; David, Frank; Marchand, Cyril

2018-04-01

Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log K D values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb. Copyright © 2018 Elsevier Ltd. All rights reserved.

Simultaneous application of chemical oxidation and extraction processes is effective at remediating soil Co-contaminated with petroleum and heavy metals.

PubMed

Yoo, Jong-Chan; Lee, Chadol; Lee, Jeung-Sun; Baek, Kitae

2017-01-15

Chemical extraction and oxidation processes to clean up heavy metals and hydrocarbon from soil have a higher remediation efficiency and take less time than other remediation processes. In batch extraction/oxidation process, 3% hydrogen peroxide (H 2 O 2 ) and 0.1 M ethylenediaminetetraacetic acid (EDTA) could remove approximately 70% of the petroleum and 60% of the Cu and Pb in the soil, respectively. In particular, petroleum was effectively oxidized by H 2 O 2 without addition of any catalysts through dissolution of Fe oxides in natural soils. Furthermore, heavy metals bound to Fe-Mn oxyhydroxides could be extracted by metal-EDTA as well as Fe-EDTA complexation due to the high affinity of EDTA for metals. However, the strong binding of Fe-EDTA inhibited the oxidation of petroleum in the extraction-oxidation sequential process because Fe was removed during the extraction process with EDTA. The oxidation-extraction sequential process did not significantly enhance the extraction of heavy metals from soil, because a small portion of heavy metals remained bound to organic matter. Overall, simultaneous application of oxidation and extraction processes resulted in highly efficient removal of both contaminants; this approach can be used to remove co-contaminants from soil in a short amount of time at a reasonable cost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Synthesis and characterization of MnS2/reduced graphene oxide nanohybrids for with photocatalytic and antibacterial activity.

PubMed

Fakhri, Ali; Kahi, Delaram Salehpour

2017-01-01

A facile one-step hydrothermal route was developed here to prepare MnS 2 /reduced graphene oxide nanohybrids. The crystal morphologies could be controlled by adjusting the solvent, surfactant, and pH of the precursor solution. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), UV-Vis absorption spectra, and photoluminescence spectra (PL), were used to characterize the structures of the samples were used to characterize the structures of the samples, and the specific surface area was determined using the Brunauer-Emmett-Teller (BET) method. The thickness of the MnS 2 nanoparticles and MnS 2 /reduced graphene oxide nanohybrids were measured to be about 20 and 5nm, respectively. The total pore volume and specific surface area were 0.540 and 1.173cm 3 g -1 and 45.91 and 98.23m 2 g -1 for pure MnS 2 and MnS 2 /r-GO hybrids, respectively. Carbophenothion as an insecticide photodegradation was used to estimate the photocatalytic activity of the MnS 2 /reduced graphene oxide nanohybrids morphologies under UV light. The Carbophenothion hardly decomposed during photolysis over a period of 45min. The rate constant, k value, for the photocatalysis of Carbophenothion by MnS 2 /reduced graphene oxide nanohybrids under UV light radiation is 0.134min -1 . The antibacterial properties of the nanohybrids were evaluated by determining their minimum inhibitory and bactericidal concentrations (MIC and MBC), using a broth microdilution assay for Escherichia coli (E. coli) bacteria. The MIC and MBC values are 4.0 and 32.0μg/mL. Copyright © 2016 Elsevier B.V. All rights reserved.

Method for carbon dioxide splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, James E.; Diver, Jr., Richard B.; Siegel, Nathan P.

A method for splitting carbon dioxide via a two-step metal oxide thermochemical cycle by heating a metal oxide compound selected from an iron oxide material of the general formula A.sub.xFe.sub.3-xO.sub.4, where 0.ltoreq.x.ltoreq.1 and A is a metal selected from Mg, Cu, Zn, Ni, Co, and Mn, or a ceria oxide compound of the general formula M.sub.aCe.sub.bO.sub.c, where 0

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE PAGES

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.; ...

2017-11-26

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.

The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300–360 °C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N 2 gas. Lastly, results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.