Residual stress within nanoscale metallic multilayer systems during thermal cycling

DOE PAGES

Economy, David Ross; Cordill, Megan Jo; Payzant, E. Andrew; ...

2015-09-21

Projected applications for nanoscale metallic multilayers will include wide temperature ranges. Since film residual stress has been known to alter system reliability, stress development within new film structures with high interfacial densities should be characterized to identify potential long-term performance barriers. To understand factors contributing to thermal stress evolution within nanoscale metallic multilayers, stress in Cu/Nb systems adhered to Si substrates was calculated from curvature measurements collected during cycling between 25 °C and 400 °C. Additionally, stress within each type of component layers was calculated from shifts in the primary peak position from in-situ heated X-ray diffraction. The effects ofmore » both film architecture (layer thickness) and layer order in metallic multilayers were tracked and compared with monolithic Cu and Nb films. Analysis indicated that the thermoelastic slope of nanoscale metallic multilayer films depends on thermal expansion mismatch, elastic modulus of the components, and also interfacial density. The layer thickness (i.e. interfacial density) affected thermoelastic slope magnitude while layer order had minimal impact on stress responses after the initial thermal cycle. When comparing stress responses of monolithic Cu and Nb films to those of the Cu/Nb systems, the nanoscale metallic multilayers show a similar increase in stress above 200 °C to the Nb monolithic films, indicating that Nb components play a larger role in stress development than Cu. Local stress calculations from X-ray diffraction peak shifts collected during heating reveal that the component layers within a multilayer film respond similarly to their monolithic counterparts.« less

Nanoscale perspective: Materials designs and understandings in lithium metal anodes

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

Lin, Dingchang; Liu, Yayuan; Pei, Allen

Li metal chemistry is a promising alternative with a much higher energy density than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technology from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies onmore » nanoscale Li nucleation/deposition. Lastly, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technology and inspires more research in the future.« less

Nanoscale perspective: Materials designs and understandings in lithium metal anodes

DOE PAGES

Lin, Dingchang; Liu, Yayuan; Pei, Allen; ...

2017-05-19

Li metal chemistry is a promising alternative with a much higher energy density than that of state-of-the-art Li-ion counterparts. However, significant challenges including safety issues and poor cyclability have severely impeded Li metal technology from becoming viable. In recent years, nanotechnologies have become increasingly important in materials design and fabrication for Li metal anodes, contributing to major progress in the field. In this review, we first introduce the main achievements in Li metal battery systems fulfilled by nanotechnologies, particularly regarding Li metal anode design and protection, ultrastrong separator engineering, safety monitoring, and smart functions. Next, we introduce recent studies onmore » nanoscale Li nucleation/deposition. Lastly, we discuss possible future research directions. We hope this review delivers an overall picture of the role of nanoscale approaches in the recent progress of Li metal battery technology and inspires more research in the future.« less

Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

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

Weinrich, Henning; Come, Jérémy; Tempel, Hermann

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topographymore » changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.« less

Metal-metal interaction mediates the iron induction of Drosophila MtnB

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

Qiang, Wenjia; Huang, Yunpeng; Wan, Zhihui

Metallothionein (MT) protein families are a class of small and universal proteins rich in cysteine residues. They are synthesized in response to heavy metal stresses to sequester the toxic ions by metal-thiolate bridges. Five MT family members, namely MtnA, MtnB, MtnC, MtnD and MtnE, have been discovered and identified in Drosophila. These five isoforms of MTs are regulated by metal responsive transcription factor dMTF-1 and play differentiated but overlapping roles in detoxification of metal ions. Previous researches have shown that Drosophila MtnB responds to copper (Cu), cadmium (Cd) and zinc (Zn). Interestingly in this study we found that Drosophila MtnBmore » expression also responds to elevated iron levels in the diet. Further investigations revealed that MtnB plays limited roles in iron detoxification, and the direct binding of MtnB to ferrous iron in vitro is also weak. The induction of MtnB by iron turns out to be mediated by iron interference of other metals, because EDTA at even a partial concentration of that of iron can suppress this induction. Indeed, in the presence of iron, zinc homeostasis is altered, as reflected by expression changes of zinc transporters dZIP1 and dZnT1. Thus, iron-mediated MtnB induction appears resulting from interrupted homeostasis of other metals such as zinc, which in turns induced MtnB expression. Metal-metal interaction may more widely exist than we expected. - Highlights: • Metallothionein B expression is regulated by iron in Drosophila melanogaster. • MtnB has limited physiological roles in iron detoxification. • Binding affinity of MtnB to iron is weak in vitro. • Induction of Drosophila MtnB by iron is mediated indirectly through metal-metal interaction.« less

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

In Vitro Biocompatibility of Nanoscale Zerovalent Iron Particles (NZVI) Synthesized using tea-polyphenols.

EPA Science Inventory

A “green” protocol was used for the rapid generation of nanoscale zerovalent iron (NZVI) particles using tea polyphenols. The NZVI particles were subsequently examined for in vitro biocompatibility using the human keratinocyte cell (HaCaT) line as a skin exposure model. The cell...

Nanoscale zero-valent metals: a review of synthesis, characterization, and applications to environmental remediation.

PubMed

Li, Lingyun; Hu, Jiwei; Shi, Xuedan; Fan, Mingyi; Luo, Jin; Wei, Xionghui

2016-09-01

Engineered nanoscale zero-valent metals (NZVMs) representing the forefront of technologies have been considered as promising materials for environmental remediation and antimicrobial effect, due to their high reducibility and strong adsorption capability. This review is focused on the methodology for synthesis of bare NZVMs, supported NZVMs, modified NZVMs, and bimetallic systems with both traditional and green methods. Recent studies have demonstrated that self-assembly methods can play an important role for obtaining ordered, controllable, and tunable NZVMs. In addition to common characterization methods, the state-of-the-art methods have been developed to obtain the properties of NZVMs (e.g., granularity, size distribution, specific surface area, shape, crystal form, and chemical bond) with the resolution down to subnanometer scale. These methods include spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), electron energy-loss spectroscopy (EELS), and near edge X-ray absorption fine structure (NEXAFS). A growing body of experimental data has proven that nanoscale zero-valent iron (NZVI) is highly effective and versatile. This article discusses the applications of NZVMs to treatment of heavy metals, halogenated organic compounds, polycyclic aromatic hydrocarbons, nutrients, radioelements, and microorganisms, using both ex situ and in situ methods. Furthermore, this paper briefly describes the ecotoxicological effects for NZVMs and the research prospects related to their synthesis, modification, characterization, and applications.

Removal of heavy metals using bentonite supported nano-zero valent iron particles

NASA Astrophysics Data System (ADS)

Zarime, Nur Aishah; Yaacob, Wan Zuhari Wan; Jamil, Habibah

2018-04-01

This study reports the composite nanoscale zero-valent iron (nZVI) which was successfully synthesized using low cost natural clay (bentonite). Bentonite composite nZVI (B-nZVI) was introduced to reduce the agglomeration of nZVI particles, thus will used for heavy metals treatment. The synthesized material was analyzed using physical, mineralogy and morphology analysis such as Brunnaer-Emmett-Teller (BET) surface area, Field Emission Scanning Electron Microscopy (FESEM), X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). The batch adsorption test of Bentonite and B-nZVI with heavy metals solutions (Pb, Cu, Cd, Co, Ni and Zn) was also conducted to determine their effectiveness in removing heavy metals. Through Batch test, B-nZVI shows the highest adsorption capacity (qe= 50.25 mg/g) compared to bentonite (qe= 27.75 mg/g). This occurred because B-nZVI can reduce aggregation of nZVI, dispersed well in bentonite layers thus it can provide more sites for adsorbing heavy metals.

Optimization of Nanoscale Zero-Valent Iron for the Remediation of Groundwater Contaminants

DTIC Science & Technology

2012-03-22

the polyelectrolyte’s adsorption to the nZVI surface via physisorption. In contrast, studies on CMC and polyacrylic acid (PAA) stabilization of nZVI...OPTIMIZATION OF NANOSCALE ZERO‒VALENT IRON FOR THE REMEDIATION OF GROUNDWATER CONTAMINANTS THESIS...Andrew W.E. McPherson, Second Lieutenant, USAF AFIT/GES/ENV/12-M01 DEPARTMENT OF THE AIR FORCE AIR UNIVERSITY AIR FORCE INSTITUTE OF

Enhanced Biogas Production from Nanoscale Zero Valent Iron-Amended Anaerobic Bioreactors

PubMed Central

Carpenter, Alexis Wells; Laughton, Stephanie N.; Wiesner, Mark R.

2015-01-01

Abstract Addition of nanoscale zero valent iron (NZVI) to anaerobic batch reactors to enhance methanogenic activity is described. Two NZVI systems were tested: a commercially available NZVI (cNZVI) slurry and a freshly synthesized NZVI (sNZVI) suspension that was prepared immediately before addition to the reactors. In both systems, the addition of NZVI increased pH and decreased oxidation/reduction potential compared with unamended control reactors. Biodegradation of a model brewery wastewater was enhanced as indicated by an increase in chemical oxygen demand removal with both sNZVI and cNZVI amendments at all concentrations tested (1.25–5.0 g Fe/L). Methane production increased for all NZVI-amended bioreactors, with a maximum increase of 28% achieved on the addition of 2.5 and 5.0 g/L cNZVI. Addition of bulk zero-valent iron resulted in only a 5% increase in methane, indicating the advantage of using the nanoscale particles. NZVI amendments further improved produced biogas by decreasing the amount of CO2 released from the bioreactor by approximately 58%. Overall, addition of cNZVI proved more beneficial than the sNZVI at equal iron concentrations, due to decreased colloidal stability and larger effective particle size of sNZVI. Although some have reported cytotoxicity of NZVI to anaerobic microorganisms, work presented here suggests that NZVI of a certain particle size and reactivity can serve as an amendment to anaerobic digesters to enhance degradation and increase the value of the produced biogas, yielding a more energy-efficient anaerobic method for wastewater treatment. PMID:26339183

Evaluating nanoscale ultra-thin metal films by means of lateral photovoltaic effect in metal-semiconductor structure.

PubMed

Zheng, Diyuan; Yu, Chongqi; Zhang, Qian; Wang, Hui

2017-12-15

Nanoscale metal-semiconductor (MS) structure materials occupy an important position in semiconductor and microelectronic field due to their abundant physical phenomena and effects. The thickness of metal films is a critical factor in determining characteristics of MS devices. How to detect or evaluate the metal thickness is always a key issue for realizing high performance MS devices. In this work, we propose a direct surface detection by use of the lateral photovoltaic effect (LPE) in MS structure, which can not only measure nanoscale thickness, but also detect the fluctuation of metal films. This method is based on the fact that the output of lateral photovoltaic voltage (LPV) is closely linked with the metal thickness at the laser spot. We believe this laser-based contact-free detection is a useful supplement to the traditional methods, such as AFM, SEM, TEM or step profiler. This is because these traditional methods are always incapable of directly detecting ultra-thin metal films in MS structure materials.

Evaluating nanoscale ultra-thin metal films by means of lateral photovoltaic effect in metal-semiconductor structure

NASA Astrophysics Data System (ADS)

Zheng, Diyuan; Yu, Chongqi; Zhang, Qian; Wang, Hui

2017-12-01

Nanoscale metal-semiconductor (MS) structure materials occupy an important position in semiconductor and microelectronic field due to their abundant physical phenomena and effects. The thickness of metal films is a critical factor in determining characteristics of MS devices. How to detect or evaluate the metal thickness is always a key issue for realizing high performance MS devices. In this work, we propose a direct surface detection by use of the lateral photovoltaic effect (LPE) in MS structure, which can not only measure nanoscale thickness, but also detect the fluctuation of metal films. This method is based on the fact that the output of lateral photovoltaic voltage (LPV) is closely linked with the metal thickness at the laser spot. We believe this laser-based contact-free detection is a useful supplement to the traditional methods, such as AFM, SEM, TEM or step profiler. This is because these traditional methods are always incapable of directly detecting ultra-thin metal films in MS structure materials.

An Iron Reservoir to the Catalytic Metal

PubMed Central

Liu, Fange; Geng, Jiafeng; Gumpper, Ryan H.; Barman, Arghya; Davis, Ian; Ozarowski, Andrew; Hamelberg, Donald; Liu, Aimin

2015-01-01

The rubredoxin motif is present in over 74,000 protein sequences and 2,000 structures, but few have known functions. A secondary, non-catalytic, rubredoxin-like iron site is conserved in 3-hydroxyanthranilate 3,4-dioxygenase (HAO), from single cellular sources but not multicellular sources. Through the population of the two metal binding sites with various metals in bacterial HAO, the structural and functional relationship of the rubredoxin-like site was investigated using kinetic, spectroscopic, crystallographic, and computational approaches. It is shown that the first metal presented preferentially binds to the catalytic site rather than the rubredoxin-like site, which selectively binds iron when the catalytic site is occupied. Furthermore, an iron ion bound to the rubredoxin-like site is readily delivered to an empty catalytic site of metal-free HAO via an intermolecular transfer mechanism. Through the use of metal analysis and catalytic activity measurements, we show that a downstream metabolic intermediate can selectively remove the catalytic iron. As the prokaryotic HAO is often crucial for cell survival, there is a need for ensuring its activity. These results suggest that the rubredoxin-like site is a possible auxiliary iron source to the catalytic center when it is lost during catalysis in a pathway with metabolic intermediates of metal-chelating properties. A spare tire concept is proposed based on this biochemical study, and this concept opens up a potentially new functional paradigm for iron-sulfur centers in iron-dependent enzymes as transient iron binding and shuttling sites to ensure full metal loading of the catalytic site. PMID:25918158

Formation and characterization of metallic iron grains in coal-based reduction of oolitic iron ore

NASA Astrophysics Data System (ADS)

Sun, Yong-sheng; Han, Yue-xin; Li, Yan-feng; Li, Yan-jun

2017-02-01

To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally reduced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the reduced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumulative frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol-1, and 922.05, respectively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.

The removal of chromium (VI) and lead (II) from groundwater using sepiolite-supported nanoscale zero-valent iron (S-NZVI).

PubMed

Fu, Rongbing; Yang, Yingpin; Xu, Zhen; Zhang, Xian; Guo, Xiaopin; Bi, Dongsu

2015-11-01

In this study, the synthesis and characterization of sepiolite-supported nanoscale zero-valent iron particles (S-NZVI) was investigated for the adsorption/reduction of Cr(VI) and Pb(II) ions. Nanoscale zero-valent iron (NZVI) supported on sepiolite was successfully used to remove Cr(VI) and Pb(II) from groundwater with high efficiency. The removal mechanism was proposed as a two-step interaction including both the physical adsorption of Cr(VI) and Pb(II) on the surface or inner layers of the sepiolite-supported NZVI particles and the subsequent reduction of Cr(VI) to Cr(III) and Pb(II) to Pb(0) by NZVI. The immobilization of the NZVI particles on the surface of sepiolite could help to overcome the disadvantage of NZVI particles, which have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both the effective surface area and reaction performance. The techniques of XRD, XPS, BET, Zeta potential, and TEM were used to characterize the S-NZVI and interaction between S-NZVI and heavy metals. The appropriate S-NZVI dosage was 1.6 g L(-1). The removal efficiency of Cr(VI) and Pb(II) by S-NZVI was not affected to any considerable extent by the presence of co-existing ions, such as H2PO4(-), SiO3(2-), Ca(2+) and HCO3(-). The Cr(VI) and Pb(II) removal kinetics followed a pseudo-first-order rate expression, and both Langmuir isotherm model and Freundlich isotherm model were proposed. The results suggested that supporting NZVI on sepiolite had the potential to become a promising technique for in situ heavy metal-contaminated groundwater remediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Redox Deposition of Nanoscale Metal Oxides on Carbon for Next-Generation Electrochemical Capacitors

DTIC Science & Technology

2013-01-01

Nanoscale Metal Oxides Sassin et al. Redox Deposition Approaches to Nanoscale Coatings of Metal Oxides Manganese Oxides. Permanganate (MnO4 ) is a versa...scalability of the permanganate carbon redox reaction for generating MnOx coatings that store charge.21 The initial study per- formed on planar graphite...the carbon surface from the aqueous permanganate solu- tion (pH∼5),29,35 evidenced by a sharp increase in solution pH and a decrease in solution

Fungal nanoscale metal carbonates and production of electrochemical materials.

PubMed

Li, Qianwei; Gadd, Geoffrey Michael

2017-09-01

Fungal biomineralization of carbonates results in metal removal from solution or immobilization within a solid matrix. Such a system provides a promising method for removal of toxic or valuable metals from solution, such as Co, Ni, and La, with some carbonates being of nanoscale dimensions. A fungal Mn carbonate biomineralization process can be applied for the synthesis of novel electrochemical materials. © 2017 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Stabilization of biosolids with nanoscale zero-valent iron (nZVI)

NASA Astrophysics Data System (ADS)

Li, Xiao-qin; Brown, Derick G.; Zhang, Wei-xian

2007-04-01

Biosolids are the treated organic residuals, also known as sludge, that are generated from domestic wastewater treatment plants. According to the USEPA, over 7 millions tons (dry weight) of biosolids are generated every year in the US by more than the 16,000 wastewater treatment plants and a large portion of these biosolids is disposed on land. Nuisance odors, the potential of pathogen transmission, and presence of toxic and persistent organic chemicals and metals in biosolids have for the most part limited the use of land applications. This paper presents zero-valent iron nanoparticles (1-100 nm) for the treatment and stabilization of biosolids. Iron nanoparticles have been shown to form stable and nonvolatile surface complexes with malodorous sulfur compounds such as hydrogen sulfide and methyl sulfides, degrade persistent organic pollutants such as PCBs and chlorinated pesticides, and sequestrate toxic metal ions such as mercury and lead. The end products from the nanoparticle reactions are iron oxides and oxyhydroxides, similar to the ubiquitous iron minerals in the environment. Due to the large surface area and high surface reactivity, only a relatively low dose (<0.1% wt) of iron nanoparticles is needed for effective biosolids stabilization. The iron nanoparticle technology may thus offer an economically and environmentally sustainable and unique solution to one of the most vexing environmental problems.

Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead.

PubMed

Kim, Hojeong; Hong, Hye-Jin; Jung, Juri; Kim, Seong-Hye; Yang, Ji-Won

2010-04-15

Nowadays, many researchers have studied the environmental application of the nanoscale zero-valent iron (nZVI) and several field applications for the groundwater remediation have been reported. Still, there are many concerns on the fate and transport of the nZVI and the corresponding risks. To avoid such concerns, it was investigated to immobilize nZVI in a support and then it was applied to degrade trichloroethylene (TCE). The nZVI and palladium-doped nZVI (Fe(0)- and Fe/Pd-alginate) were immobilized in the alginate bead where ferric and barium ions are used as the cross-linking cations of the bead. According to TEM (transmission electron microscopy), the size of the immobilized ZVI was as small as a few nanometers. From the surface analysis of the Fe/Pd-alginate, it is found that the immobilized nZVI has the core-shell structure. The core is composed of single crystal Fe(0), while most of irons on the surface are oxidized to Fe(3+). When 50 g/L of Fe/Pd-alginate (3.7 g Fe/L) was introduced to the aqueous solution, >99.8% of TCE was removed and the release of metal from the support was <3% of the loaded iron. The removal of TCE by Fe/Pd-alginate followed pseudo-first-order kinetics. The observed pseudo-first-order reaction constant (k(obs)) of Fe/Pd-alginate was 6.11 h(-1) and the mass normalized rate constant (k(m)) was 1.6 L h(-1) g(-1). The k(m) is the same order of magnitude with that of iron nanoparticles. In conclusion, it is considered that Fe/Pd-alginate can be used efficiently in the treatment of chlorinated solvent. 2009 Elsevier B.V. All rights reserved.

Dechlorination of disinfection by-product monochloroacetic acid in drinking water by nanoscale palladized iron bimetallic particle.

PubMed

Chen, Chao; Wang, Xiangyu; Chang, Ying; Liu, Huiling

2008-01-01

Nanoscale palladized iron (Pd/Fe) bimetallic particles were prepared by reductive deposition method. The particles were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscope (SEM), transmission electron microscope (TEM), and Brunauer-Emmett-Teller-nitrogen (BET-N2) method. Data obtained from those methods indicated that nanoscale Pd/Fe bimetallic particles contained alpha-Fe0. Detected Pd to Fe ratio by weight (Pd/Fe ratio) was close to theoretical value. Spherical granules with diameter of 47 +/- 11.5 nm connected with one another to form chains and the chains composed nanoscale Pd/Fe bimetallic particles. Specific surface area of particles was 51 m2/g. The factors, such as species of reductants, Pd/Fe ratio, dose of nanoscale Pd/Fe bimetallic particles added into solutions, solution initial pH, and a variety of solvents were studied. Dechlorination effect of monochloroacetic acid by different reductants followed the trend: nanoscale Pd/Fe bimetallic particles of 0.182% Pd/Fe > nanoscale Fe > reductive Fe. When the Pd/Fe ratio was lower than 0.083%, increasing Pd/Fe ratio would increase dechlorination efficiency (DE) of MCAA. When the Pd/Fe ratio was higher than 0.083%, increasing Pd/Fe ratio caused a decrease in DE. Adding more nanoscale Pd/Fe bimetallic particles to solution would enhance DE. The DE of MCAA decreased as initial pH of solution increased.

Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLs

NASA Technical Reports Server (NTRS)

Reinhart, Debra R. (Inventor); Clausen, Christian (Inventor); Gelger, Cherie L. (Inventor); Quinn, Jacqueline (Inventor); Brooks, Kathleen (Inventor)

2006-01-01

A zero-valent metal emulsion is used to dehalogenate solvents, such as pooled dense non-aqueous phase liquids (DNAPLs), including trichloroethylene (TCE). The zero-valent metal emulsion contains zero-valent metal particles, a surfactant, oil and water, The preferred zero-valent metal particles are nanoscale and microscale zero-valent iron particles.

Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLS

NASA Technical Reports Server (NTRS)

Reinhart, Debra R. (Inventor); Clausen, Christian (Inventor); Geiger, Cherie L. (Inventor); Quinn, Jacqueline (Inventor); Brooks, Kathleen (Inventor)

2003-01-01

A zero-valent metal emulsion is used to dehalogenate solvents, such as pooled dense non-aqueous phase liquids (DNAPLs), including trichloroethylene (TCE). The zero-valent metal emulsion contains zero-valent metal particles, a surfactant, oil and water. The preferred zero-valent metal particles are nanoscale and microscale zero-valent iron particles

Nanoscale growth twins in sputtered metal films

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

Misra, Amit; Anderoglu, Osman; Hoagland, Richard G

2008-01-01

We review recent studies on the mechanical properties of sputtered Cu and 330 stainless steel films with {l_brace}1 1 1{r_brace} nanoscale growth twins preferentially oriented perpendicular to growth direction. The mechanisms of formation of growth twins during sputtering and the deformation mechanisms that enable usually high strengths in nanotwinned structures are highlighted. Growth twins in sputtered films possess good thermal stability at elevated temperature, providing an approach to extend the application of high strength nanostructured metals to higher temperatures.

In situ remediation of hexavalent chromium contaminated soil by CMC-stabilized nanoscale zero-valent iron composited with biochar.

PubMed

Zhang, Runyuan; Zhang, Nuanqin; Fang, Zhanqiang

2018-03-01

In this study, the remediation experiments were performed outdoors in natural conditions. Carboxymethyl cellulose (CMC)-stabilized nanoscale zero-valent iron (CMC-nZVI), biochar (BC) and CMC-stabilized nanoscale zero-valent iron composited with biochar (CMC-nZVI/BC) were synthesized and investigated for their effect on the in situ remediation of hexavalent chromium [Cr(VI)] contaminated soil and the concentration of available iron was tested after the remediation, compared with the untreated soil. The results of toxicity characteristic leaching procedure (TCLP) test showed that CMC-nZVI and CMC-nZVI/BC used as remediation materials could obviously improve the remediation rate of Cr contaminated soil and when the ratio of CMC-nZVI to Fe 0 was 2.5 g/Kg, the leachability of Cr(VI) and Cr total can be reduced by 100% and 95.8% simultaneously. Moreover, sequential extraction procedure (SEP) showed that most exchangeable Cr converted to carbonate-bound and Fe-Mn oxides-bound, reducing the availability and leachability of Cr in the soil.

Nanoscale zero-valent iron (nZVI): aspects of the core-shell structure and reactions with inorganic species in water.

PubMed

Yan, Weile; Herzing, Andrew A; Kiely, Christopher J; Zhang, Wei-Xian

2010-11-25

Aspects of the core-shell model of nanoscale zero-valent iron (nZVI) and their environmental implications were examined in this work. The structure and elemental distribution of nZVI were characterized by X-ray energy-dispersive spectroscopy (XEDS) with nanometer-scale spatial resolution in an aberration-corrected scanning transmission electron microscope (STEM). The analysis provides unequivocal evidence of a layered structure of nZVI consisting of a metallic iron core encapsulated by a thin amorphous oxide shell. Three aqueous environmental contaminants, namely Hg(II), Zn(II) and hydrogen sulfide, were studied to probe the reactive properties and the surface chemistry of nZVI. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis of the reacted particles indicated that Hg(II) was sequestrated via chemical reduction to elemental mercury. On the other hand, Zn(II) removal was achieved via sorption to the iron oxide shell followed by zinc hydroxide precipitation. Hydrogen sulfide was immobilized on the nZVI surface as disulfide (S(2)(2-)) and monosulfide (S(2-)) species. Their relative abundance in the final products suggests that the retention of hydrogen sulfide occurs via reactions with the oxide shell to form iron sulfide (FeS) and subsequent conversion to iron disulfide (FeS(2)). The results presented herein highlight the multiple reactive pathways permissible with nZVI owing to its two functional constituents. The core-shell structure imparts nZVI with manifold functional properties previously unexamined and grants the material with potentially new applications. Copyright © 2010 Elsevier B.V. All rights reserved.

Iron phosphate compositions for containment of hazardous metal waste

DOEpatents

Day, Delbert E.

1998-01-01

An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P.sub.2 O.sub.5 and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe.sup.3+ provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided.

Iron phosphate compositions for containment of hazardous metal waste

DOEpatents

Day, D.E.

1998-05-12

An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P{sub 2}O{sub 5} and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe{sup 3+} provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided. 21 figs.

Nanoscale electrical characteristics of metal (Au, Pd)-graphene-metal (Cu) contacts

NASA Astrophysics Data System (ADS)

Ruffino, F.; Meli, G.; Grimaldi, M. G.

2016-01-01

Free-standing graphene presents exceptional physical properties (as a high carrier mobility) making it the ideal candidate for the next generation nanoelectronics. However, when graphene layers are inserted in real electronics devices, metal contacting is required. The metal-graphene interaction significantly affects the graphene electrical properties, drastically changing its behavior with respect to the free-standing configuration. So, this work presents an experimental study on the nanoscale electric characteristics of metal/graphene/metal contacts. In particular, starting from single-layer graphene grown on Cu foil we deposited on the graphene surface two different metal films (Au or Pd) and the Au/graphene/Cu and Pd/graphene/Cu current-voltage characteristics are acquired, on the nanometric scale, by the conductive atomic force microscopy. Both systems presented a current voltage rectifying behavior. However, the Au/graphene/Cu system conducts significantly at negative applied bias (graphene behaves as a p-type semiconductor in a meta/semiconductor contact), while in the Pd/graphene/Cu at positive applied bias (graphene behaves as a n-type semiconductor in a metal/semiconductor contact). This difference is discussed on the basis of the band energy diagram at the metal/graphene interface and the modification of the graphene Fermi level due to the Au/graphene or Pd/graphene interaction.

Nanoscale zerovalent iron-mediated degradation of DDT in soil.

PubMed

Han, Yuling; Shi, Nan; Wang, Huifang; Pan, Xiong; Fang, Hua; Yu, Yunlong

2016-04-01

Nanoscale zerovalent iron (nZVI)-mediated degradation of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) was investigated in a spiked soil under different conditions (iron sources, iron dosage, soil moisture, temperature, and soil types) and DDT-contaminated field. The degradation efficiency of p,p'-DDT by nZVI and nZVI coated with sodium oleate (SO-nZVI) was much higher than that by nZVI coated with polyimide (PI-nZVI). The rapid degradation of p,p'-DDT by nZVI only occurred in flooded soil. The degradation half-life of p,p'-DDT decreased significantly from 58.3 to 27.6 h with nZVI dosage from 0.5 to 2.0% and from 46.5 to 32.0 h with temperature from 15 to 35 °C. The degradation efficiency of p,p'-DDT by nZVI differed in Jinhua (JH), Jiaxing (JX), Xiaoshan (XS), Huajiachi (HJC), and Heilongjiang (HLJ) soils. A good correlation was found between the degradation half-life of p,p'-DDT and multiple soil properties. The probable nZVI-mediated degradation pathway of p,p'-DDT in soil was proposed as DDT → DDD/DDE → DDNS → DDOH based on the metabolites identified by GC-MS. The in situ degradation efficiency of residual DDTs in a contaminated field was profoundly enhanced by the addition of nZVI as compared to the control. It is concluded that nZVI might be an efficient agent for the remediation of DDT-contaminated soil under anaerobic environment.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

Nanoscale Zero-Valent Iron Decorated on Bentonite/Graphene Oxide for Removal of Copper Ions from Aqueous Solution.

PubMed

Shao, Jicheng; Yu, Xiaoniu; Zhou, Min; Cai, Xiaoqing; Yu, Chuang

2018-06-04

The removal efficiency of Cu(II) in aqueous solution by bentonite, graphene oxide (GO), and nanoscale iron decorated on bentonite (B-nZVI) and nanoscale iron decorated on bentonite/graphene oxide (GO-B-nZVI) was investigated. The results indicated that GO-B-nZVI had the best removal efficiency in different experimental environments (with time, pH, concentration of copper ions, and temperature). For 16 hours, the removal efficiency of copper ions was 82% in GO-B-nZVI, however, it was 71% in B-nZVI, 26% in bentonite, and 18% in GO. Bentonite, GO, B-nZVI, and GO-B-nZVI showed an increased removal efficiency of copper ions with the increase of pH under a certain pH range. The removal efficiency of copper ions by GO-B-nZVI first increased and then fluctuated slightly with the increase of temperature, while B-nZVI and bentonite increased and GO decreased slightly with the increase of temperature. Lorentz-Transmission Electron Microscope (TEM) images showed the nZVI particles of GO-B-nZVI dispersed evenly with diameters ranging from 10 to 86.93 nm. Scanning electron microscope (SEM) images indicated that the nanoscale iron particles were dispersed evenly on bentonite and GO with no obvious agglomeration. The q e,cal (73.37 mg·g -1 and 83.89 mg·g -1 ) was closer to the experimental value q e,exp according to the pseudo-second-order kinetic model. The q m of B-nZVI and GO-B-nZVI were 130.7 mg·g -1 and 184.5 mg·g -1 according to the Langmuir model.

Nanoscale Inhomogeneous Superconductivity in Fe(Te1-xSex) Probed by Nanostructure Transport.

PubMed

Yue, Chunlei; Hu, Jin; Liu, Xue; Sanchez, Ana M; Mao, Zhiqiang; Wei, Jiang

2016-01-26

Among iron-based superconductors, the layered iron chalcogenide Fe(Te1-xSex) is structurally the simplest and has attracted considerable attention. It has been speculated from bulk studies that nanoscale inhomogeneous superconductivity may inherently exist in this system. However, this has not been directly observed from nanoscale transport measurements. In this work, through simple micromechanical exfoliation and high-precision low-energy ion milling thinning, we prepared Fe(Te0.5Se0.5) nanoflakes with various thicknesses and systematically studied the correlation between the thickness and superconducting phase transition. Our result revealed a systematic thickness-dependent evolution of superconducting transition. When the thickness of the Fe(Te0.5Se0.5) flake is reduced to less than the characteristic inhomogeneity length (around 12 nm), both the superconducting current path and the metallicity of the normal state in Fe(Te0.5Se0.5) atomic sheets are suppressed. This observation provides the first transport evidence for the nanoscale inhomogeneous nature of superconductivity in Fe(Te1-xSex).

Magnetic solid phase extraction of typical polycyclic aromatic hydrocarbons from environmental water samples with metal organic framework MIL-101 (Cr) modified zero valent iron nano-particles.

PubMed

Zhou, Qingxiang; Lei, Man; Wu, Yalin; Yuan, Yongyong

2017-03-03

Metal-organic framework material has been paid more attention because of its good physical and chemical properties. Nanoscale zero valent iron is also in the center of concern recently. Combination of their merits will give impressive results. Present study firstly synthesized a new magnetic nanomaterial nano-scale zero valent iron-functionalized metal-organic framworks MIL-101 (Fe@MIL-101) by co-precipitation method. The morphology and structure of the as-prepared Fe@MIL-101 were characterized by transmission electron microscopy and X-ray diffraction, etc. The experimental results showed that Fe@MIL-101 earned good adsorption ability to polycyclic aromatic hydrocarbons. The limits of detection of developed magnetic solid phase extraction were all below 0.064μgL -1 and precision can be expressed as relative standard deviation (RSD, %) and which was better than 4.4% (n=6). The real water analysis indicated that the spiked recoveries were satisfied, and Fe@MIL-101 earned excellent reusability. All these demonstrated that Fe@MIL-101 exhibited excellent adsorption capability to polycyclic aromatic hydrocarbons and would be a good adsorbent for development of new monitoring methods for environmental pollutants. Copyright © 2017 Elsevier B.V. All rights reserved.

Removal of Cr(VI) by nanoscale zero-valent iron (nZVI) from soil contaminated with tannery wastes.

PubMed

Singh, Ritu; Misra, Virendra; Singh, Rana Pratap

2012-02-01

The illegal disposal of tannery wastes at Rania, Kanpur has resulted in accumulation of hexavalent chromium [Cr(VI)], a toxic heavy metal in soil posing risk to human health and environment. 27 soil samples were collected at various depths from Rania for the assessment of Cr(VI) level in soil. Out of 27 samples, five samples had shown significant level of Cr(VI) with an average concentration of 15.84 mg Kg(-1). Varied doses of nanoscale zero-valent iron (nZVI) were applied on Cr(VI) containing soil samples for remediation of Cr(VI). Results showed that 0.10 g L(-1) nZVI completely reduces Cr(VI) within 120 min following pseudo first order kinetics. Further, to test the efficacy of nZVI in field, soil windrow experiments were performed at the contaminated site. nZVI showed significant Cr(VI) reduction at field also, indicating it an effective tool for managing sites contaminated with Cr(VI).

Higher concentrations of nanoscale zero-valent iron (nZVI) in soil induced rice chlorosis due to inhibited active iron transportation.

PubMed

Wang, Jie; Fang, Zhanqiang; Cheng, Wen; Yan, Xiaomin; Tsang, Pokeung Eric; Zhao, Dongye

2016-03-01

In this study, the effects of concentrations 0, 100, 250, 500, 750 and 1000 mg kg(-1) of nanoscale zero-valent iron (nZVI) on germination, seedlings growth, physiology and toxicity mechanisms were investigated. The results showed that nZVI had no effect on germination, but inhibited the rice seedlings growth in higher concentrations (>500 mg kg(-1) nZVI). The highest suppression rate of the length of roots and shoots reached 46.9% and 57.5%, respectively. The 1000mg kg(-1) nZVI caused the highest suppression rates for chlorophyll and carotenoids, at 91.6% and 85.2%, respectively. In addition, the activity of antioxidant enzymes was altered by the translocation of nanoparticles and changes in active iron content. Visible symptoms of iron deficiency were observed at higher concentrations, at which the active iron content decreased 61.02% in the shoots, but the active iron content not decreased in roots. Interestingly, the total and available amounts of iron in the soil were not less than those in the control. Therefore, the plants iron deficiency was not caused by (i) deficiency of available iron in the soil and (ii) restraint of the absorption that plant takes in the available iron, while induced by (ⅲ) the transport of active iron from the root to the shoot was blocked. The cortex tissues were seriously damaged by nZVI which was transported from soil to the root, these were proved by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). This current study shows that the mechanism of iron deficiency in rice seedling was due to transport of active iron from the root to the shoot blocked, which was caused by the uptake of nZVI. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced nitrate-nitrogen removal by modified attapulgite-supported nanoscale zero-valent iron treating simulated groundwater.

PubMed

Dong, Lei; Lin, Li; Li, Qingyun; Huang, Zhuo; Tang, Xianqiang; Wu, Min; Li, Chao; Cao, Xiaohuan; Scholz, Miklas

2018-05-01

Attapulgite (or palygorskite) is a magnesium aluminium phyllosilicate. Modified attapulgite-supported nanoscale zero-valent iron (NZVI) was created by a liquid-phase reduction method and then applied for nitrate-nitrogen (NO 3 -N) removal (transformation) in simulated groundwater. Nanoscale zero-valent iron was sufficiently dispersed on the surface of thermally modified attapulgite. The NO 3 -N removal efficiency reached up to approximately 83.8% with an initial pH values of 7.0. The corresponding thermally modified attapulgite-supported nanoscale zero-valent iron (TATP-NZVI) and NO 3 -N concentrations were 2.0 g/L and 20 mg/L respectively. Moreover, 72.1% of the water column NO 3 -N was converted to ammonium-nitrogen (NH 4 -N) within 6 h. The influence of environmental boundary conditions including dissolved oxygen (DO) concentration, light illumination and water temperature on NO 3 -N removal was also investigated with batch experiments. The results indicated that the DO concentration greatly impacted on NO 3 -N removal in the TATP-NZVI-contained solution, and the NO 3 -N removal efficiencies were 58.5% and 83.3% with the corresponding DO concentrations of 9.0 and 0.3 mg/L after 6 h of treatment, respectively. Compared to DO concentrations, no significant (p > 0.05) effect of light illumination on NO 3 -N removal and NH 4 -N generation was detected. The water temperature also has great importance concerning NO 3 -N reduction, and the removal efficiency of NO 3 -N at 25 °C was 1.25 times than that at 15 °C. For groundwater, therefore, environmental factors such as water temperature, anaerobic conditions and darkness could influence the NO 3 -N removal efficiency when TATP-NZVI is present. This study also demonstrated that TATP-NZVI has the potential to be developed as a suitable material for direct remediation of NO 3 -N-contaminated groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

PubMed

Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

2014-03-01

Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances. Copyright © 2014. Published by Elsevier B.V.

Nanoscale zerovalent iron (nZVI) at environmentally relevant concentrations induced multigenerational reproductive toxicity in Caenorhabditis elegans.

PubMed

Yang, Ying-Fei; Chen, Pei-Jen; Liao, Vivian Hsiu-Chuan

2016-05-01

Nanoscale zerovalent iron (nZVI) is widely used with large scale for environmental remediation for in situ or ex situ applications. The potential impact of nZVI on biota at environmentally relevant concentrations needs to be elucidated. In this study, the reproductive toxicities of three irons species: carboxymethyl cellulose (CMC)-stabilized nZVI, nanoscale iron oxide (nFe3O4), and ferrous ion (Fe(II)aq) in the soil-dwelling nematode Caenorhabditis elegans were examined. In addition, the generational transfer of reproductive toxicity of CMC-nZVI on C. elegans was investigated. The results showed that CMC-nZVI, nFe3O4, and Fe(II)aq did not cause significant mortality after 24 h exposure at the examined concentrations. Reproductive toxicity assays revealed that CMC-nZVI, nFe3O4, and Fe(II)aq significantly decreased offsprings in parental generation (F0) in accompany with the increased intracellular reactive oxygen species (ROS). Furthermore, the reproductive toxicity of CMC-nZVI at environmentally relevant concentrations was transferrable from the F0 to the F1 and F2 generations, but then recovered in the F3 and F4 generations. Further evidence showed that total irons were accumulated in the F0 and F1 generations of C. elegans after CMC-nZVI parental exposure. This study demonstrated that environmentally relevant concentrations of CMC-nZVI induced multigenerational reproductive toxicity which can be ascribed to its high production of ROS in F0 generation, toxicity of Fe(II)aq, and iron accumulation in C. elegans. Since nZVI is widely used for environmental remediation, considering the multigenerational toxicity, this study thus implicates a potential environmental risk of nZVI-induced nanotoxicity in the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal ion binding to iron oxides

NASA Astrophysics Data System (ADS)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Improving proton therapy by metal-containing nanoparticles: nanoscale insights

PubMed Central

Schlathölter, Thomas; Eustache, Pierre; Porcel, Erika; Salado, Daniela; Stefancikova, Lenka; Tillement, Olivier; Lux, Francois; Mowat, Pierre; Biegun, Aleksandra K; van Goethem, Marc-Jan; Remita, Hynd; Lacombe, Sandrine

2016-01-01

The use of nanoparticles to enhance the effect of radiation-based cancer treatments is a growing field of study and recently, even nanoparticle-induced improvement of proton therapy performance has been investigated. Aiming at a clinical implementation of this approach, it is essential to characterize the mechanisms underlying the synergistic effects of nanoparticles combined with proton irradiation. In this study, we investigated the effect of platinum- and gadolinium-based nanoparticles on the nanoscale damage induced by a proton beam of therapeutically relevant energy (150 MeV) using plasmid DNA molecular probe. Two conditions of irradiation (0.44 and 3.6 keV/μm) were considered to mimic the beam properties at the entrance and at the end of the proton track. We demonstrate that the two metal-containing nanoparticles amplify, in particular, the induction of nanosize damages (>2 nm) which are most lethal for cells. More importantly, this effect is even more pronounced at the end of the proton track. This work gives a new insight into the underlying mechanisms on the nanoscale and indicates that the addition of metal-based nanoparticles is a promising strategy not only to increase the cell killing action of fast protons, but also to improve tumor targeting. PMID:27143877

Aging effects on chemical transformation and metal(loid) removal by entrapped nanoscale zero-valent iron for hydraulic fracturing wastewater treatment.

PubMed

Sun, Yuqing; Lei, Cheng; Khan, Eakalak; Chen, Season S; Tsang, Daniel C W; Ok, Yong Sik; Lin, Daohui; Feng, Yujie; Li, Xiang-Dong

2018-02-15

In this study, alginate and polyvinyl alcohol (PVA)-alginate entrapped nanoscale zero-valent iron (nZVI) was tested for structural evolution, chemical transformation, and metals/metalloids removal (Cu(II), Cr(VI), Zn(II), and As(V)) after 1-2month passivation in model saline wastewaters from hydraulic fracturing. X-ray diffraction analysis confirmed successful prevention of Fe 0 corrosion by polymeric entrapment. Increasing ionic strength (I) from 0 to 4.10M (deionized water to Day-90 fracturing wastewater (FWW)) with prolonged aging time induced chemical instability of alginate due to dissociation of carboxyl groups and competition for hydrogen bonding with nZVI, which caused high Na (7.17%) and total organic carbon (24.6%) dissolution from PVA-alginate entrapped nZVI after 2-month immersion in Day-90 FWW. Compared to freshly-made beads, 2-month aging of PVA-alginate entrapped nZVI in Day-90 FWW promoted Cu(II) and Cr(VI) uptake in terms of the highest removal efficiency (84.2% and 70.8%), pseudo-second-order surface area-normalized rate coefficient k sa (2.09×10 -1 Lm -2 h -1 and 1.84×10 -1 Lm -2 h -1 ), and Fe dissolution after 8-h reaction (13.9% and 8.45%). However, the same conditions inhibited Zn(II) and As(V) sequestration in terms of the lowest removal efficiency (31.2% and 39.8%) by PVA-alginate nZVI and k sa (4.74×10 -2 Lm -2 h -1 and 6.15×10 -2 Lm -2 h -1 ) by alginate nZVI. The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in metals/metalloids removal by entrapped nZVI after aging was attributed to distinctive removal mechanisms: (i) enhanced Cu(II) and Cr(VI) removal by nZVI reduction with accelerated electron transfer after pronounced dissolution of non-conductive polymeric immobilization matrix; (ii) suppressed Zn(II) and As(V) removal by nZVI adsorption due to restrained mass transfer after blockage of surface-active micropores. Entrapped nZVI was chemically fragile and should be properly stored

Evolution of nanoscale zero-valent iron (nZVI) in water: Microscopic and spectroscopic evidence on the formation of nano- and micro-structured iron oxides.

PubMed

Liu, Airong; Liu, Jing; Han, Jinhao; Zhang, Wei-Xian

2017-01-15

Knowledge on the transformation of nanoscale zero-valent iron (nZVI) in water is essential to predict its surface chemistry including surface charge, colloidal stability and aggregation, reduction and sorption of organic contaminants, heavy metal ions and other pollutants in the environment. In this work, transmission electronic microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy are applied to study the compositional and structural evolution of nZVI under oxic and anoxic conditions. Under anoxic conditions, the core-shell structure of nZVI is well maintained even after 72h, and the corrosion products usually contain a mixture of wustite (FeO), goethite (α-FeOOH) and akaganeite (β-FeOOH). Under oxic conditions, the core-shell structure quickly collapses to flakes or acicular-shaped structures with crystalline lepidocrocite (γ-FeOOH) as the primary end product. This work provides detailed information and fills an important knowledge gap on the physicochemical characteristics and structural evolution of engineered nanomaterials in the environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Interactions between microbial iron reduction and metal geochemistry: effect of redox cycling on transition metal speciation in iron bearing sediments.

PubMed

Cooper, D Craig; Picardal, Flynn F; Coby, Aaron J

2006-03-15

Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respectto Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HCl insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a -3x increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by approximately 12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These

System and method for producing metallic iron

DOEpatents

Englund, David J.; Schlichting, Mark; Meehan, John; Crouch, Jeremiah; Wilson, Logan

2014-07-29

A method of production of metallic iron nodules comprises assembling a hearth furnace having a moveable hearth comprising refractory material and having a conversion zone and a fusion zone, providing a hearth material layer comprising carbonaceous material on the refractory material, providing a layer of reducible material comprising and iron bearing material arranged in discrete portions over at least a portion of the hearth material layer, delivering oxygen gas into the hearth furnace to a ratio of at least 0.8:1 ponds of oxygen to pounds of iron in the reducible material to heat the conversion zone to a temperature sufficient to at least partially reduce the reducible material and to heat the fusion zone to a temperature sufficient to at least partially reduce the reducible material, and heating the reducible material to form one or more metallic iron nodules and slag.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Method and system for producing metallic iron nuggets

DOEpatents

Iwasaki, Iwao; Kiesel, Richard F.; Englund, David J; Hendrickson, Dave

2012-12-18

A method and system for producing metallic iron nuggets may include providing multiple layers of agglomerates, such as briquettes, balls and extrusions, of a reducible mixture of reducing material (such as carbonaceous material) and of a reducible iron bearing material (such as iron oxide) on a hearth material layer (such as carbonaceous material) and providing a coarse overlayer of carbonaceous material over at least some of the agglomerates. Heating the agglomerates of reducible mixture to 1425.degree. C. or 1400.degree. C. or 1375.degree. C. results in formation of an intermediate product of one or more metallic iron nuggets, which may have a sulfur content of less than 0.03%, and slag, which may have less than 5% mass MgO, which may have a ratio of percent by weight sulfur in the slag over percent by weight sulfur in the metallic nuggets of at least about 12 or at least about 15.

Mobility, Deposition and Remobilization of pre-Synthesis Stabilized Nano-scale Zero Valent Iron in Long Column Experiments

NASA Astrophysics Data System (ADS)

de Boer, C. V.; O'Carroll, D. M.; Sleep, B.

2014-12-01

Reactive zero-valent iron is currently being used for remediation of contaminated groundwater. Permeable reactive barriers are the current state-of-the-practice method for using zero-valent iron. Instead of an excavated trench filled with granular zero-valent iron, a relatively new and promising method is the injection of a nano-scale zero-valent iron colloid suspension (nZVI) into the subsurface using injection wells. One goal of nZVI injection can be to deposit zero valent iron in the aquifer and form a reactive permeable zone which is no longer bound to limited depths and plume treatment, but can also be used directly at the source. It is very important to have a good understanding of the transport behavior of nZVI during injection as well as the fate of nZVI after injection due to changes in the flow regime or water chemistry changes. So far transport was mainly tested using commercially available nZVI, however these studies suggest that further work is required as commercial nZVI was prone to aggregation, resulting in low physical stability of the suspension and very short travel distances in the subsurface. In the presented work, nZVI is stabilized during synthesis to significantly increase the physical suspension stability. To improve our understanding of nZVI transport, the feasibility for injection into various porous media materials and controlled deposition, a suite of column experiments are conducted. The column experiments are performed using a long 1.5m column and a novel nZVI measuring technique. The measuring technique was developed to non-destructively determine the concentration of nano-scale iron during the injection. It records the magnetic susceptibility, which makes it possible to get transient nZVI retention profiles along the column. These transient nZVI retention profiles of long columns provide unique insights in the transport behavior of nZVI which cannot be obtained using short columns or effluent breakthrough curves.

Metal regeneration of iron chelates in nitric oxide scrubbing

DOEpatents

Chang, S.G.; Littlejohn, D.; Shi, Y.

1997-08-19

The present invention relates to a process of using metal particles to reduce NO to NH{sub 3}. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: (a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20 and 90 C to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution. 34 figs.

Metal regeneration of iron chelates in nitric oxide scrubbing

DOEpatents

Chang, Shih-Ger; Littlejohn, David; Shi, Yao

1997-08-19

The present invention relates to a process of using metal particles to reduce NO to NH.sub.3. More specifically, the invention concerns an improved process to regenerate iron (II) (CHELATE) by reduction of iron (II) (CHELATE) (NO) complex, which process comprises: a) contacting an aqueous solution containing iron (II) (CHELATE) (NO) with metal particles at between about 20.degree. and 90.degree. C. to reduce NO present, produce ammonia or an ammonium ion, and produce free iron (II) (CHELATE) at a pH of between about 3 and 8. The process is useful to remove NO from flue gas and reduce pollution.

Nanoscale electron manipulation in metals with intense THz electric fields

NASA Astrophysics Data System (ADS)

Takeda, Jun; Yoshioka, Katsumasa; Minami, Yasuo; Katayama, Ikufumi

2018-03-01

Improved control over the electromagnetic properties of metals on a nanoscale is crucial for the development of next-generation nanoelectronics and plasmonic devices. Harnessing the terahertz (THz)-electric-field-induced nonlinearity for the motion of electrons is a promising method of manipulating the local electromagnetic properties of metals, while avoiding undesirable thermal effects and electronic transitions. In this review, we demonstrate the manipulation of electron delocalization in ultrathin gold (Au) films with nanostructures, by intense THz electric-field transients. On increasing the electric-field strength of the THz pulses, the transmittance in the THz-frequency region abruptly decreases around the percolation threshold. The observed THz-electric-field-induced nonlinearity is analysed, based on the Drude-Smith model. The results suggest that ultrafast electron delocalization occurs by electron tunnelling across the narrow insulating bridge between the Au nanostructures, without material breakdown. In order to quantitatively discuss the tunnelling process, we perform scanning tunnelling microscopy with carrier-envelope phase (CEP)-controlled single-cycle THz electric fields. By applying CEP-controlled THz electric fields to the 1 nm nanogap between a metal nanotip and graphite sample, many electrons could be coherently driven through the quantum tunnelling process, either from the nanotip to the sample or vice versa. The presented concept, namely, electron tunnelling mediated by CEP-controlled single-cycle THz electric fields, can facilitate the development of nanoscale electron manipulation, applicable to next-generation ultrafast nanoelectronics and plasmonic devices.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

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

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Structural evolution of nanoscale metallic glasses during high-pressure torsion: A molecular dynamics analysis

NASA Astrophysics Data System (ADS)

Feng, S. D.; Jiao, W.; Jing, Q.; Qi, L.; Pan, S. P.; Li, G.; Ma, M. Z.; Wang, W. H.; Liu, R. P.

2016-11-01

Structural evolution in nanoscale Cu50Zr50 metallic glasses during high-pressure torsion is investigated using molecular dynamics simulations. Results show that the strong cooperation of shear transformations can be realized by high-pressure torsion in nanoscale Cu50Zr50 metallic glasses at room temperature. It is further shown that high-pressure torsion could prompt atoms to possess lower five-fold symmetries and higher potential energies, making them more likely to participate in shear transformations. Meanwhile, a higher torsion period leads to a greater degree of forced cooperative flow. And the pronounced forced cooperative flow at room temperature under high-pressure torsion permits the study of the shear transformation, its activation and characteristics, and its relationship to the deformations behaviors. This research not only provides an important platform for probing the atomic-level understanding of the fundamental mechanisms of high-pressure torsion in metallic glasses, but also leads to higher stresses and homogeneous flow near lower temperatures which is impossible previously.

Nanoscale zero-valent iron (nZVI) for the treatment of concentrated Cu(II) wastewater: a field demonstration.

PubMed

Li, Shaolin; Wang, Wei; Yan, Weile; Zhang, Wei-xian

2014-03-01

A field demonstration was conducted to assess the feasibility of nanoscale zero-valent iron (nZVI) for the treatment of wastewater containing high levels of Cu(II). Pilot tests were performed at a printed-circuit-board manufacturing plant, treating 250,000 L of wastewater containing 70 mg L(-1) Cu(II) with a total of 55 kg of nZVI. A completely mixed reactor of 1,600 L was operated continuously with flow rates ranging from 1000 to 2500 L h(-1). The average Cu(II) removal efficiency was greater than 96% with 0.20 g L(-1) nZVI and a hydraulic retention time of 100 min. The nZVI reactor achieved a remarkably high volumetric loading rate of 1876 g Cu per m(3) per day for Cu(II) removal, surpassing the loading rates of conventional technologies by more than one order of magnitude. The average removal capacity of nZVI for Cu(II) was 0.343 g Cu per gram of Fe. The Cu(II) removal efficiency can be reliably regulated by the solution Eh, which in turn is a function of nZVI input and hydraulic retention time. The ease of separation and recycling of nZVI contribute to process up-scalability and cost effectiveness. Cu(II) was reduced to metallic copper and cuprite (Cu2O). The end product is a valuable composite of iron and copper (∼20-25%), which can partially offset the treatment costs.

System and method for producing metallic iron nodules

DOEpatents

Bleifuss, Rodney L [Grand Rapids, MN; Englund, David J [Bovey, MN; Iwasaki, Iwao [Grand Rapids, MN; Lindgren, Andrew J [Grand Rapids, MN; Kiesel, Richard F [Hibbing, MN

2011-09-20

A method for producing metallic iron nodules by assembling a shielding entry system to introduce coarse carbonaceous material greater than 6 mesh in to the furnace atmosphere at location(s) where the temperature of the furnace atmosphere adjacent at least partially reduced reducible iron bearing material is between about 2200 and 2650.degree. F. (1200 and 1450.degree. C.), the shielding entry system adapted to inhibit emission of infrared radiation from the furnace atmosphere and seal the furnace atmosphere from exterior atmosphere while introducing coarse carbonaceous material greater than 6 mesh into the furnace to be distributed over the at least partially reduced reducible iron bearing material, and heating the covered at least partially reduced reducible iron bearing material in a fusion atmosphere to assist in fusion and inhibit reoxidation of the reduced material during fusion to assist in fusion and inhibit reoxidation of the reduced material in forming metallic iron nodules.

Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media

NASA Astrophysics Data System (ADS)

Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E.

2014-08-01

Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50 = 2.4 μm) are investigated in column tests using columns of 40 cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5 mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from - 62 mV to - 80 mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions.

Transport of carbon colloid supported nanoscale zero-valent iron in saturated porous media.

PubMed

Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E

2014-08-01

Injection of nanoscale zero-valent iron (nZVI) has recently gained great interest as emerging technology for in-situ remediation of chlorinated organic compounds from groundwater systems. Zero-valent iron (ZVI) is able to reduce organic compounds and to render it to less harmful substances. The use of nanoscale particles instead of granular or microscale particles can increase dechlorination rates by orders of magnitude due to its high surface area. However, classical nZVI appears to be hampered in its environmental application by its limited mobility. One approach is colloid supported transport of nZVI, where the nZVI gets transported by a mobile colloid. In this study transport properties of activated carbon colloid supported nZVI (c-nZVI; d50=2.4μm) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from -62mV to -80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxidation of nanoscale zero-valent iron under sufficient and limited dissolved oxygen: Influences on aggregation behaviors.

PubMed

Jiang, Danlie; Hu, Xialin; Wang, Rui; Yin, Daqiang

2015-03-01

Oxidations of nanoscale zero-valent iron (nZVI) under aerobic (dissolved oxygen≈8mgL(-1)) and anaerobic (dissolved oxygen <3mgL(-1)) conditions were simulated, and their influences on aggregation behaviors of nZVI were investigated. The two oxidation products were noted as HO-nZVI (nZVI oxidized in highly oxygenated water) and LO-nZVI (nZVI oxidized in lowly oxygenated water) respectively. The metallic iron of the oxidized nZVI was almost exhausted (Fe(0)≈8±5%), thus magnetization mainly depended on magnetite content. Since sufficient dissolved oxygen led to the much less magnetite (∼15%) in HO-nZVI than that in LO-nZVI (>90%), HO-nZVI was far less magnetic (Ms=88kAm(-1)) than LO-nZVI (Ms=365kAm(-1)). Consequently, HO-nZVI formed small agglomerates (228±10nm), while LO-nZVI tended to form chain-like aggregations (>1μm) which precipitated rapidly. Based on the EDLVO theory, we suggested that dissolved oxygen level determined aggregation morphologies by controlling the degree of oxidation and the magnitude of magnetization. Then the chain-like alignment of LO-nZVI would promote further aggregation, but the agglomerate morphology of HO-nZVI would eliminate magnetic forces and inhibit the aggregation while HO-nZVI remained magnetic. Our results indicated the fine colloidal stability of HO-nZVI, which might lead to the great mobility in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Towards "Precision Mining" of wastewater: Selective recovery of Cu from acid mine drainage onto diatomite supported nanoscale zerovalent iron particles.

PubMed

Crane, R A; Sapsford, D J

2018-07-01

This paper introduces the concept of 'Precision Mining' of metals which can be defined as a process for the selective in situ uptake of a metal from a material or media, with subsequent retrieval and recovery of the target metal. In order to demonstrate this concept nanoscale zerovalent iron (nZVI) was loaded onto diatomaceous earth (DE) and tested for the selective uptake of Cu from acid mine drainage (AMD) and subsequent release. Batch experiments were conducted using the AMD and nZVI-DE at 4.0-16.0 g/L. Results demonstrate nZVI-DE as highly selective for Cu removal with >99% uptake recorded after 0.25 h when using nZVI-DE concentrations ≥12.0 g/L, despite appreciable concentrations of numerous other metals in the AMD, namely: Co, Ni, Mn and Zn. Cu uptake was maintained in excess of 4 and 24 h when using nZVI-DE concentrations of 12.0 and 16.0 g/L respectively. Near-total Cu release from the nZVI-DE was then recorded and attributed to the depletion of the nZVI component and the subsequent Eh, DO and pH recovery. This novel Cu uptake and release mechanism, once appropriately engineered, holds great promise as a novel 'Precision Mining' process for the rapid and selective Cu recovery from acidic wastewater, process effluents and leach liquors. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Improvements in nanoscale zero-valent iron production by milling through the addition of alumina

NASA Astrophysics Data System (ADS)

Ribas, D.; Cernik, M.; Martí, V.; Benito, J. A.

2016-07-01

A new milling procedure for a cost-effective production of nanoscale zero-valent iron for environmental remediation is presented. Conventional ball milling of iron in an organic solvent as Mono Ethylene Glycol produces flattened iron particles that are unlikely to break even after very long milling times. With the aim of breaking down these iron flakes, in this new procedure, further milling is carried out by adding an amount of fine alumina powder to the previously milled solution. As the amount of added alumina increases from 9 to 54 g l-1, a progressive decrease of the presence of flakes is observed. In the latter case, the appearance of the particles formed by fragments of former flakes is rather homogeneous, with most of the final nanoparticles having an equivalent diameter well below 1 µm and with an average particle size in solution of around 400 nm. An additional increase of alumina content results in a highly viscous solution showing worse particle size distribution. Milled particles, in the case of alumina concentrations of 54 g l-1, have a fairly large specific surface area and high Fe(0) content. These new particles show a very good Cr(VI) removal efficiency compared with other commercial products available. This good reactivity is related to the absence of an oxide layer, the large amount of superficial irregularities generated by the repetitive fracture process during milling and the presence of a fine nanostructure within the iron nanoparticles.

Large area nanoscale metal meshes for use as transparent conductive layers.

PubMed

Jin, Yuanhao; Li, Qunqing; Chen, Mo; Li, Guanhong; Zhao, Yudan; Xiao, Xiaoyang; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan

2015-10-21

We report on the experimental realization of using super-aligned carbon nanotubes (SACNTs) as etching masks for the fabrication of large area nanoscale metal meshes. This method can easily be extended to different metals on both rigid and flexible substrates. The as-fabricated metal meshes, including the ones made of gold, copper, and aluminum, are suitable for use as transparent conductive layers (TCLs). The metal meshes, which are similar to the SACNT networks in their dimensional features of tens of nanometers, exhibit compatible performance in terms of optical transmittance and sheet resistance. Moreover, because the metal meshes are fabricated as an integrated material, there is no junction resistance between the interconnected metal nanostructures, which markedly lowers their sheet resistance at high temperatures. The fabrication of such an effective etching mask involves a simple drawing process of the SACNT networks prepared and a common deposition process. This approach should be easy to extend to various research fields and has broad prospects in commercial applications.

Impact of biogenic nanoscale metals Fe, Cu, Zn and Se on reproductive LV chickens

NASA Astrophysics Data System (ADS)

Khiem Nguyen, Quy; Dieu Nguyen, Duy; Kien Nguyen, Van; Thinh Nguyen, Khac; Chau Nguyen, Hoai; Tin Tran, Xuan; Nguyen, Huu Cuong; Tien Phung, Duc

2015-09-01

Using biogenic nanoscale metals (Fe, Cu, ZnO, Se) to supplement into diet premix of reproductive LV (a Vietnamese Luong Phuong chicken breed) chickens resulted in certain improvement of poultry farming. The experimental data obtained showed that the farming indices depend mainly on the quantity of nanocrystalline metals which replaced the inorganic mineral component in the feed premix. All four experimental groups with different quantities of the replacement nano component grew and developed normally with livability reaching 91 to 94%, hen’s bodyweight at 38 weeks of age and egg weight ranged from 2.53-2.60 kg/hen and 50.86-51.55 g/egg, respectively. All these farming indices together with laying rate, egg productivity and chick hatchability peaked at group 5 with 25% of nanoscale metals compared to the standard inorganic mineral supplement, while feed consumption was lowest. The results also confirmed that nanocrystalline metals Fe, Cu, ZnO and Se supplemented to chicken feed were able to decrease inorganic minerals in the diet premixes at least four times, allowing animals to more effectively absorb feed minerals, consequently decreasing environmental pollution risks.

Manufacturing and Application of Metalized Ore-Coal Pellets in Synthetic Pig Iron Smelting

NASA Astrophysics Data System (ADS)

Nokhrina, O. I.; Rozhikhina, I. D.; Khodosov, I. E.

2016-08-01

The article presents research data on manufacturing and application of metalized ore-coal pellets in synthetic pig iron smelting. A technology of pellets metallization by means of solid-phase reduction of iron from oxides using hematite-magnetite iron ore and low-caking coal as raw materials is described. Industrial testing of replacing 10, 15, and 20% of waste metal by the metalized ore-coal pellets in the coreless induction furnace IST-1 is described. Optimal temperature and time conditions of feeding the metalized pellets into the furnace in smelting pig iron of SCh-40-60 grade are determined.

Nanoscale patterning of two metals on silicon surfaces using an ABC triblock copolymer template.

PubMed

Aizawa, Masato; Buriak, Jillian M

2006-05-03

Patterning technologically important semiconductor interfaces with nanoscale metal films is important for applications such as metallic interconnects and sensing applications. Self-assembling block copolymer templates are utilized to pattern an aqueous metal reduction reaction, galvanic displacement, on silicon surfaces. Utilization of a triblock copolymer monolayer film, polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO), with two blocks capable of selective transport of different metal complexes to the surface (PEO and P2VP), allows for chemical discrimination and nanoscale patterning. Different regions of the self-assembled structure discriminate between metal complexes at the silicon surface, at which time they undergo the spontaneous reaction at the interface. Gold deposition from gold(III) compounds such as HAuCl4(aq) in the presence of hydrofluoric acid mirrors the parent block copolymer core structure, whereas silver deposition from Ag(I) salts such as AgNO3(aq) does the opposite, localizing exclusively under the corona. By carrying out gold deposition first and silver second, sub-100-nm gold features surrounded by silver films can be produced. The chemical selectivity was extended to other metals, including copper, palladium, and platinum. The interfaces were characterized by a variety of methods, including scanning electron microscopy, scanning Auger microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy.

Kinetic research on dechlorinating dichlorobenzene in aqueous system by nano-scale nickel/iron loaded with CMC/NFC hydrogel.

PubMed

Wan, Xiao-Fang; Guo, Congbao; Liu, Yu; Chai, Xin-Sheng; Li, Youming; Chen, Guangxue

2018-03-01

In this study, we reported on the nano-scale nickel/iron particles loaded in carboxymethyl/nanofibrillated cellulose (CMC/NFC) hydrogel for the dechlorination of o-dichlorobenzene (DCB) in aqueous solution. The biodegradable hydrogel may provide an ideal supporting material for fastening the bimetallic nano-scale particles, which was examined and characterized by TEM, SEM-EDX, FT-IR and BET. The performance of the selected bimetallic particles was evaluated by conducting the dechlorination of DCB in the solution under different reaction conditions (e.g., pH, dosage of nickel/iron nanoparticles and temperature). The results showed that about 70% of DCB could be dechlorinated at 20 °C in 8 h, which indicated that the immobilized reactive material had a high reduction activity when Ni/Fe loading dosage in the hydrogel (18 wt%) was considered. Moreover, the reduction behavior agreed to the pseudo-first order reaction, in which the dechlorination rate was irrelative to the pH aqueous solution. A kinetic model for predicting the concentration of DCB during the reduction reaction was established based on the experimental data. Copyright © 2017 Elsevier Ltd. All rights reserved.

Wet-chemical synthesis of nanoscale iron boride, XAFS analysis and crystallisation to α-FeB.

PubMed

Rades, Steffi; Kornowski, Andreas; Weller, Horst; Albert, Barbara

2011-06-20

The reaction of lithium tetrahydridoborate and iron bromide in high boiling ether as reaction medium produces an ultrafine, pyrophoric and magnetic precipitate. X-ray and electron diffraction proved the product to be amorphous. According to X-ray absorption fine structure spectroscopy (XAFS) the precipitate has FeB structure up to nearly two coordination spheres around an iron absorber atom. Transmission electron microscopy (TEM) confirms the ultrafine powder to be nanoscale. Subsequent annealing at 450 °C causes the atoms to arrange in a more distinct FeB structure, and further thermal treatment to 1050 °C extends the local structure to the α-modification of FeB. Between 1050 °C and 1500 °C α-FeB is transformed into β-FeB. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of Subsurface Heterogeneities on nano-Scale Zero Valent Iron Transport

NASA Astrophysics Data System (ADS)

Krol, M. M.; Sleep, B. E.; O'Carroll, D. M.

2011-12-01

Nano-scale zero valent iron (nZVI) has been applied as a remediation technology at sites contaminated with chlorinated compounds and heavy metals. Although laboratory studies have demonstrated high reactivity for the degradation of target contaminants, the success of nZVI in the field has been limited due to poor subsurface mobility. When injected into the subsurface, nZVI tends to aggregate and be retained by subsurface soils. As such nZVI suspensions need to be stabilized for increased mobility. However, even with stabilization, soil heterogeneities can still lead to non-uniform nZVI transport, resulting in poor distribution and consequently decreased degradation of target compounds. Understanding how nZVI transport can be affected by subsurface heterogeneities can aid in improving the technology. This can be done with the use of a numerical model which can simulate nZVI transport. In this study CompSim, a finite difference groundwater model, is used to simulate the movement of nZVI in a two-dimensional domain. CompSim has been shown in previous studies to accurately predict nZVI movement in the subsurface, and is used in this study to examine the impact of soil heterogeneity on nZVI transport. This work also explores the impact of different viscosities of the injected nZVI suspensions (corresponding to different stabilizing polymers) and injection rates on nZVI mobility. Analysis metrics include travel time, travel distance, and average nZVI concentrations. Improving our understanding of the influence of soil heterogeneity on nZVI transport will lead to improved field scale implementation and, potentially, to more effective remediation of contaminated sites.

Method and system for producing metallic iron nuggets

DOEpatents

Iwasaki, Iwao; Lindgren, Andrew J.; Kiesel, Richard F.

2013-06-25

Method and system for producing metallic nuggets includes providing reducible mixture of reducing material (such as carbonaceous material) and reducible iron bearing material (such as iron oxide) that may be arranged in discrete portions, such as mounds or briquettes, on at least a portion of a hearth material layer (such as carbonaceous material). A coarse overlayer of carbonaceous material may be provided over at least some of the discrete portions. Heating the reducible mixture to 1425.degree. C. or 1400.degree. C. or 1375.degree. C. results in formation of an intermediate product of one or more metallic iron nuggets, which may have a sulfur content of less than 0.03%, and slag, which may have less than 5% mass MgO, which may have a ratio of percent by weight sulfur in the slag over percent by weight sulfur in the metallic nuggets of at least about 12 or at least about 15.

Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

PubMed

Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

2012-12-01

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

Reduced Uranium Phases Produced from Anaerobic Reaction with Nanoscale Zerovalent Iron.

PubMed

Tsarev, Sergey; Collins, Richard N; Fahy, Adam; Waite, T David

2016-03-01

Nanoscale zerovalent iron (nZVI) has shown potential to be an effective remediation agent for uranium-contaminated subsurface environments, however, the nature of the reaction products and their formation kinetics have not been fully elucidated over a range of environmentally relevant conditions. In this study, the oxygen-free reaction of U(VI) with varying quantities of nZVI was examined at pH 7 in the presence of both calcium and carbonate using a combination of X-ray absorption spectroscopy, X-ray diffraction and transmission electron microscopy. It was observed that the structure of the reduced U solid phases was time dependent and largely influenced by the ratio of nZVI to U in the system. At the highest U:Fe molar ratio examined (1:4), nanoscale uraninite (UO2) was predominantly formed within 1 day of reaction. At lower U:Fe molar ratios (1:21), evidence was obtained for the formation of sorbed U(IV) and U(V) surface complexes which slowly transformed to UO2 nanoparticles that were stable for up to 1 year of anaerobic incubation. After 8 days of reaction at the lowest U:Fe molar ratio examined (1:110), sorbed U(IV) was still the major form of U associated with the solid phase. Regardless of the U:Fe molar ratio, the anaerobic corrosion of nZVI resulted in the slow formation of micron-sized fibrous chukanovite (Fe2(OH)2CO3) particles.

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.

Overcoming nanoscale friction barriers in transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Cammarata, Antonio; Polcar, Tomas

2017-08-01

We study the atomic contributions to the nanoscale friction in layered M X2 (M =Mo , W; X =S , Se, Te) transition metal dichalcogenides by combining ab initio techniques with group-theoretical analysis. Starting from stable atomic configurations, we propose a computational method, named normal-modes transition approximation (NMTA), to individuate possible sliding paths from only the analysis of the phonon modes of the stable geometry. The method provides a way to decompose the atomic displacements realizing the layer sliding in terms of phonon modes of the stable structure, so as to guide the selection and tuning of specific atomic motions promoting M X2 sheets gliding, and to adjust the corresponding energy barrier. The present results show that main contributions to the nanoscale friction are due to few low frequency phonon modes, corresponding to rigid shifts of M X2 layers. We also provide further evidences that a previously reported Ti-doped MoS2 phase is a promising candidate as new material with enhanced tribologic properties. The NMTA approach can be exploited to tune the energetic and the structural features of specific phonon modes, and, thanks to its general formulation, can also be applied to any solid state system, irrespective of the chemical composition and structural topology.

Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron.

PubMed

Zhang, Zhi-Yong; Lu, Mang; Zhang, Zhong-Zhi; Xiao, Meng; Zhang, Min

2012-12-01

In this study, nanoscale zero-valent iron (NZVI) particles were synthesized and used for the reductive dehalogenation of short chain chlorinated paraffins (SCCPs) in the laboratory. The results show that the dechlorination rate of chlorinated n-decane (CP(10)) by NZVI increased with decreased solution pH. Increasing the loading of NZVI enhanced the dechlorination rate of CP(10). With an increase in temperature, the degradation rate increased. The reduction of CP(10) by NZVI was accelerated with increasing the concentration of humic acid up to 15 mg/L but then was inhibited. The dechlorination of CP(10) within the initial 18 h followed pseudo-first order rate model. The formation of intermediate products indicates a stepwise dechlorination pathway of SCCPs by NZVI. The carbon chain length and chlorination degree of SCCPs have a polynominal impact on dechlorination reactions. Copyright © 2012 Elsevier B.V. All rights reserved.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Linkage of iron elution and dissolved oxygen consumption with removal of organic pollutants by nanoscale zero-valent iron: Effects of pH on iron dissolution and formation of iron oxide/hydroxide layer.

PubMed

Fujioka, Nanae; Suzuki, Moe; Kurosu, Shunji; Kawase, Yoshinori

2016-02-01

The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

Recent advances in nanoscale-metal assisted biochar derived from waste biomass used for heavy metals removal.

PubMed

Ho, Shih-Hsin; Zhu, Shishu; Chang, Jo-Shu

2017-12-01

Pollution of heavy metals (HMs) is a detrimental treat to human health and need to be cleaned up in a proper way. Biochar (BC), a low-cost and "green" adsorbent, has attracted significant attention due to its considerable HMs removal capacity. In particular, nano-metals have recently been used to assist BC in improving its reactivity, surface texture and magnetism. Synthesis methods and metal precursors greatly influence the properties and structures of the nanocomposites, thereby affecting their HMs removal performance. This review presents advances in synthesis methods, formation mechanisms and surface characteristics of BC nanocomposites, along with the discussions on HMs removal mechanisms and the effects of environmental factors on HMs removal efficiency. Performance of using BC nanocomposites to remediate real HMs-containing wastewater and issues associated with its process scale-up are also discussed. This review aims to provide useful information to facilitate the development of HMs removal by nanoscale-metal assisted BC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Recovery of indium ions by nanoscale zero-valent iron

NASA Astrophysics Data System (ADS)

Chen, Wen; Su, Yiming; Wen, Zhipan; Zhang, Yalei; Zhou, Xuefei; Dai, Chaomeng

2017-03-01

Indium and its compounds have plenty of industrial applications and high demand. Therefore, indium recovery from various industrial effluents is necessary. It was sequestered by nanoscale zero-valent iron (nZVI) whose size mainly ranged from 50 to 70 nm. Adsorption kinetics and isotherm, influence of pH, and ionic strength were thoroughly investigated. The reaction process was well fitted to a pseudo second-order model, and the maximum adsorption capacity of In(III) was 390 mg In(III)/g nZVI similar to 385 mg In(III)/g nZVI at 298 K calculated by Langmuir model. The mole ratio of Fe(II) released to In(III) immobilized was 3:2, which implied a special chemical process of co-precipitation combined Fe(OH)2 with In(OH)3. Transmission electron microscopy with an energy-disperse X-ray (TEM-EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize surface morphology, corrosion products, and valence state of indium precipitate formed on nanoparticles. The structural evolution changed from core-shell structure of iron oxide to sheet structure of co-precipitation, to sphere structure that hydroxide gradually dissolved as the pH decreased, and to cavity structures for the pH continually decreased. Furthermore, below pH 4.7, the In(III) enrichment was inhibited for the limited capacity of co-precipitation. Also, it was found that Ca2+ and HPO4 2- have more negative influence on In(III) recovery compared with Na+, NO3 -, HCO3 -, and SO4 2-. Therefore, the In(III) recovery can be described by a mechanism which consists of adsorption, co-precipitation, and reduction and was over 78% even after 3 cycles. The results confirmed that it was applicable to employ nZVI for In(III) immobilization.

Surveying the South Pole-Aitken basin magnetic anomaly for remnant impactor metallic iron

USGS Publications Warehouse

Cahill, Joshua T.S.; Hagerty, Justin J.; Lawrence, David M.; Klima, Rachel L.; Blewett, David T.

2014-01-01

The Moon has areas of magnetized crust ("magnetic anomalies"), the origins of which are poorly constrained. A magnetic anomaly near the northern rim of South Pole-Aitken (SPA) basin was recently postulated to originate from remnant metallic iron emplaced by the SPA basin-forming impactor. Here, we remotely examine the regolith of this SPA magnetic anomaly with a combination of Clementine and Lunar Prospector derived iron maps for any evidence of enhanced metallic iron content. We find that these data sets do not definitively detect the hypothesized remnant metallic iron within the upper tens of centimeters of the lunar regolith.

Release of iron, zinc, and lead from common iron construction bars and zinc metallic bars in water solutions and meals.

PubMed

Lechtig, Aarón; Lòpez de Romaña, Daniel; Boy, Erick; Vargas, Alejandro; Rosas del Portal, Mauricio; Huaylinos, María Luisa

2007-12-01

The use of iron pots has decreased the prevalence of anemia. To investigate the release of iron, zinc, and lead from metallic iron and zinc bars incubated in water and in meals. Iron, zinc, and lead concentrations were measured at different incubation conditions in water and in meals. The iron concentration in water was 1.26 mg/L after incubation with one iron bar at pH 7 and 100 degrees C for 20 minutes and in meals was 0.97 mg per 100 g of wet meals, rich in phytate, cooking at 100 degrees C during 20 minutes. The maximum contents were 7720 mg/L of iron and 1826 mg/L of zinc in vinegar at pH 3 and 20 degrees C after 90 and 32 days, respectively. Lead was released from the bars, but at concentrations well below the upper tolerable limits. In outreach populations, the use of iron and zinc metallic bars in water and meals could contribute to sustainable, very low-cost prevention of iron and zinc deficiencies, and home-fortified vinegar could be used for treatment of both deficiencies. Field trials should be performed to determine the impact that the use of iron and zinc metallic bars in water and meals might have on the iron and zinc status of population groups.

A simple route to diverse noble metal-decorated iron oxide nanoparticles for catalysis

NASA Astrophysics Data System (ADS)

Walker, Joan M.; Zaleski, Jeffrey M.

2016-01-01

Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic activity for the reduction of 4-nitrophenol (knorm = 2 × 107 s-1 mol(Pd)-1 5 × 106 s-1 mol(Au)-1 5 × 105 s-1 mol(PtAg)-1 7 × 105 s-1 mol(Ag)-1). These rates are the highest reported for nano-sized comparables, and are competitive with mesoparticles of similar composition. Due to their magnetic response, the particles are also suitable for magnetic recovery and maintain >99% conversion for at least four cycles. Using this synthetic route, Fe3O4@SiO2-M particles show great promise for further development as a precursor to complicated anisotropic materials or for applications ranging from nanocatalysis to biomedical sensing.Developing facile synthetic routes to multifunctional nanoparticles combining the magnetic properties of iron oxides with the optical and catalytic utility of noble metal particles remains an important goal in realizing the potential of hybrid nanomaterials. To this end, we have developed a single route to noble metal-decorated magnetic nanoparticles (Fe3O4@SiO2-M M = Au, Pd, Ag, and PtAg) and characterized them by HRTEM and STEM/EDX imaging to reveal their nanometer size (16 nm Fe3O4 and 1-5 nm M seeds) and uniformity. This represents one of the few examples of genuine multifunctional particles on the nanoscale. We show that these hybrid structures have excellent catalytic

Intraparticle reduction of arsenite (As(III)) by nanoscale zerovalent iron (nZVI) investigated with In Situ X-ray absorption spectroscopy.

PubMed

Yan, Weile; Vasic, Relja; Frenkel, Anatoly I; Koel, Bruce E

2012-07-03

While a high efficiency of contaminant removal by nanoscale zerovalent iron (nZVI) has often been reported for several contaminants of great concern, including aqueous arsenic species, the transformations and translocation of contaminants at and within the nanoparticles are not clearly understood. By analysis using in situ time-dependent X-ray absorption spectroscopy (XAS) of the arsenic core level for nZVI in anoxic As(III) solutions, we have observed that As(III) species underwent two stages of transformation upon adsorption at the nZVI surface. The first stage corresponds to breaking of As-O bonds at the particle surface, and the second stage involves further reduction and diffusion of arsenic across the thin oxide layer enclosing the nanoparticles, which results in arsenic forming an intermetallic phase with the Fe(0) core. Extended X-ray absorption fine-structure (EXAFS) data from experiments conducted at different iron/arsenic ratios indicate that the reduced arsenic species tend to be enriched at the surface of the Fe(0) core region and had limited mobility into the interior of the metal core within the experimental time frame (up to 22 h). Therefore, there was an accumulation of partially reduced arsenic at the Fe(0)/oxide interface when a relatively large arsenic content was present in the solid phase. These results illuminate the role of intraparticle diffusion and reduction in affecting the chemical state and spatial distribution of arsenic in nZVI materials.

Process for removing technetium from iron and other metals

DOEpatents

Leitnaker, J.M.; Trowbridge, L.D.

1999-03-23

A process for removing technetium from iron and other metals comprises the steps of converting the molten, alloyed technetium to a sulfide dissolved in manganese sulfide, and removing the sulfide from the molten metal as a slag. 4 figs.

Characterization of preferential flow paths between boreholes in fractured rock using a nanoscale zero-valent iron tracer test

NASA Astrophysics Data System (ADS)

Chuang, Po-Yu; Chia, Yeeping; Liou, Ya-Hsuan; Teng, Mao-Hua; Liu, Ching-Yi; Lee, Tsai-Ping

2016-11-01

Recent advances in borehole geophysical techniques have improved characterization of cross-hole fracture flow. The direct detection of preferential flow paths in fractured rock, however, remains to be resolved. In this study, a novel approach using nanoscale zero-valent iron (nZVI or `nano-iron') as a tracer was developed for detecting fracture flow paths directly. Generally, only a few rock fractures are permeable while most are much less permeable. A heat-pulse flowmeter can be used to detect changes in flow velocity for delineating permeable fracture zones in the borehole and providing the design basis for the tracer test. When nano-iron particles are released in an injection well, they can migrate through the connecting permeable fracture and be attracted to a magnet array when arriving in an observation well. Such an attraction of incoming iron nanoparticles by the magnet can provide quantitative information for locating the position of the tracer inlet. A series of field experiments were conducted in two wells in fractured rock at a hydrogeological research station in Taiwan, to test the cross-hole migration of the nano-iron tracer through permeable connected fractures. The fluid conductivity recorded in the observation well confirmed the arrival of the injected nano-iron slurry. All of the iron nanoparticles attracted to the magnet array in the observation well were found at the depth of a permeable fracture zone delineated by the flowmeter. This study has demonstrated that integrating the nano-iron tracer test with flowmeter measurement has the potential to characterize preferential flow paths in fractured rock.

Use of bimodal carbon distribution in compacts for producing metallic iron nodules

DOEpatents

Iwasaki, Iwao

2012-10-16

A method for use in production of metallic iron nodules comprising providing a reducible mixture into a hearth furnace for the production of metallic iron nodules, where the reducible mixture comprises a quantity of reducible iron bearing material, a quantity of first carbonaceous reducing material of a size less than about 28 mesh of an amount between about 65 percent and about 95 percent of a stoichiometric amount necessary for complete iron reduction of the reducible iron bearing material, and a quantity of second carbonaceous reducing material with an average particle size greater than average particle size of the first carbonaceous reducing material and a size between about 3 mesh and about 48 mesh of an amount between about 20 percent and about 60 percent of a stoichiometric amount of necessary for complete iron reduction of the reducible iron bearing material.

Use of bimodal carbon distribution in compacts for producing metallic iron nodules

DOEpatents

Iwasaki, Iwao

2014-04-08

A method for use in production of metallic iron nodules comprising providing a reducible mixture into a hearth furnace for the production of metallic iron nodules, where the reducible mixture comprises a quantity of reducible iron bearing material, a quantity of first carbonaceous reducing material of a size less than about 28 mesh of an amount between about 65 percent and about 95 percent of a stoichiometric amount necessary for complete iron reduction of the reducible iron bearing material, and a quantity of second carbonaceous reducing material with an average particle size greater than average particle size of the first carbonaceous reducing material and a size between about 3 mesh and about 48 mesh of an amount between about 20 percent and about 60 percent of a stoichiometric amount of necessary for complete iron reduction of the reducible iron bearing material.

Characterization of Nano-scale Aluminum Oxide Transport through Porous Media

NASA Astrophysics Data System (ADS)

Norwood, S.; Reynolds, M.; Miao, Z.; Brusseau, M. L.; Johnson, G. R.

2011-12-01

Colloidal material (including that in the nanoparticle size range) is naturally present in most subsurface environments. Mobilization of these colloidal materials via particle disaggregation may occur through abrupt changes in flow rate and/or via chemical perturbations, such as rapid changes in ionic strength or solution pH. While concentrations of natural colloidal materials in the subsurface are typically small, those concentrations may be greatly increased at contaminated sites such as following the application of metal oxides for groundwater remediation efforts. Additionally, while land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers, biosolids have been shown to contain a significant fraction of organic and inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of nano-scale colloidal materials through the soil column and their potential participation in the facilitated transport of contaminants, such as heavy metals and emerging pollutants. The purpose of this study was to investigate the transport behavior of aluminum oxide (Al2O3) nanoparticles through porous media. The impacts of pH, ionic strength, pore-water velocity (i.e., residence time), and aqueous-phase concentration on transport was investigated. All experiments were conducted with large injection pulses to fully characterize the impact of long-term retention and transport behavior relevant for natural systems wherein multiple retention processes may be operative. The results indicate that the observed nonideal transport behavior of the nano-scale colloids is influenced by multiple retention mechanisms/processes. Given the ubiquitous nature of these nano-scale colloids in the environment, a clear understanding of their transport and fate is necessary in further resolving the potential for

Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe.

PubMed

Mueller, Nicole C; Braun, Jürgen; Bruns, Johannes; Černík, Miroslav; Rissing, Peter; Rickerby, David; Nowack, Bernd

2012-02-01

Nanoscale zero valent iron (NZVI) is emerging as a new option for the treatment of contaminated soil and groundwater targeting mainly chlorinated organic contaminants (e.g., solvents, pesticides) and inorganic anions or metals. The purpose of this article is to give a short overview of the practical experience with NZVI applications in Europe and to present a comparison to the situation in the USA. Furthermore, the reasons for the difference in technology use are discussed. The results in this article are based on an extensive literature review and structured discussions in an expert workshop with experts from Europe and the USA. The evaluation of the experiences was based on a SWOT (strength, weakness, opportunity, threat) analysis. There are significant differences in the extent and type of technology used between NZVI applications in Europe and the USA. In Europe, only three full-scale remediations with NZVI have been carried out so far, while NZVI is an established treatment method in the USA. Bimetallic particles and emulsified NZVI, which are extensively used in the USA, have not yet been applied in Europe. Economic constraints and the precautionary attitude in Europe raise questions regarding whether NZVI is a cost-effective method for aquifer remediation. Challenges to the commercialization of NZVI include mainly non-technical aspects such as the possibility of a public backlash, the fact that the technology is largely unknown to consultants, governments and site owners as well as the lack of long-term experiences. Despite these concerns, the results of the current field applications with respect to contaminant reduction are promising, and no major adverse impacts on the environment have been reported so far. It is thus expected that these trials will contribute to promoting the technology in Europe.

A field investigation on transport of carbon-supported nanoscale zero-valent iron (nZVI) in groundwater.

PubMed

Busch, J; Meißner, T; Potthoff, A; Bleyl, S; Georgi, A; Mackenzie, K; Trabitzsch, R; Werban, U; Oswald, S E

2015-10-01

The application of nanoscale zero-valent iron (nZVI) for subsurface remediation of groundwater contaminants is a promising new technology, which can be understood as alternative to the permeable reactive barrier technique using granular iron. Dechlorination of organic contaminants by zero-valent iron seems promising. Currently, one limitation to widespread deployment is the fast agglomeration and sedimentation of nZVI in colloidal suspensions, even more so when in soils and sediments, which limits the applicability for the treatment of sources and plumes of contamination. Colloid-supported nZVI shows promising characteristics to overcome these limitations. Mobility of Carbo-Iron Colloids (CIC) - a newly developed composite material based on finely ground activated carbon as a carrier for nZVI - was tested in a field application: In this study, a horizontal dipole flow field was established between two wells separated by 5.3m in a confined, natural aquifer. The injection/extraction rate was 500L/h. Approximately 1.2kg of CIC was suspended with the polyanionic stabilizer carboxymethyl cellulose. The suspension was introduced into the aquifer at the injection well. Breakthrough of CIC was observed visually and based on total particle and iron concentrations detected in samples from the extraction well. Filtration of water samples revealed a particle breakthrough of about 12% of the amount introduced. This demonstrates high mobility of CIC particles and we suggest that nZVI carried on CIC can be used for contaminant plume remediation by in-situ formation of reactive barriers. Copyright © 2015 Elsevier B.V. All rights reserved.

Microscopic iron metal on glass and minerals - A tool for studying regolith maturity

NASA Technical Reports Server (NTRS)

Allen, C. C.; Morris, R. V.; Lauer, H. V., Jr.; Mckay, D. S.

1993-01-01

A novel method of producing mixtures of glass or minerals with iron metal is presented. A portion of the Fe(2+) in basaltic glass and minerals can be reduced to metal in a few hours at 1100 C and an oxygen fugacity well below the iron-wustite buffer. Part of the iron metals forms rounded submicrometer blebs on the surfaces and in some cases within the grains. A concentration of such blebs equivalent to 20-30 percent of a grain's surface area can totally dominate the reflectance spectra of basaltic glass, pyroxene, and olivine. The production of optically opaque iron metal blebs, combined with the decline in Fe(2+), affects the glass and mineral reflectance spectra in three ways: by lowering the overall reflectivity, reducing the spectral contrast of absorption features, and producing a continuum with a general rise in reflectivity toward longer wavelengths.

Adsorption of Hg(II) and Pb(II) ions by nanoscale zero valent iron supported on ostrich bone ash in a fixed-bed column system.

PubMed

Amiri, Mohammad Javad; Abedi-Koupai, Jahangir; Eslamian, Saeid

2017-07-01

In this research, ostrich bone ash (OBA) was modified with nanoscale zerovalent iron (nZVI) particles and applied as a novel composite adsorbent (OBA/nZVI) for dynamic adsorption/reduction of Hg(II) and Pb(II) ions in a fixed-bed column system. Entrapment of nZVI in OBA beads barricades the particles from oxidation and aggregation. The dynamic behavior of metal ions removal by OBA/nZVI was assessed as a function of inlet flow rates, bed height, initial pollutants concentration and pH. The synthesized OBA/nZVI composite was characterized by several physicochemical techniques. Increase in pH and bed height and decrease in flow rates and initial metal concentration resulted in delay of breakthrough time. OBA breakthrough profile is sharper than the OBA/nZVI breakthrough curve for both metal ions and the breakthrough times increase in the order OBA/nZVI-Hg(II) > OBA/nZVI-Pb(II) > OBA-Pb(II) > OBA-Hg(II). Based on the experiment results, redox reaction is expected to occur to a certain extent, as the standard reduction potentials of Hg(II) and Pb(II) are more than that of Fe(II). From a practical point of view, the OBA/nZVI could be applied as a material to remove Hg(II) and Pb(II) ions from natural surface and ground water with a pH value of 5-9.

Nanoscale Skyrmions in a Nonchiral Metallic Multiferroic: Ni 2MnGa

DOE PAGES

Phatak, Charudatta; Heinonen, Olle; De Graef, Marc; ...

2016-05-17

Magnetic skyrmions belong to a set of topologically nontrivial spin textures at the nanoscale that have received increased attention due to their emergent behavior and novel potential spintronic applications. Discovering materials systems that can host skyrmions at room temperature in the absence of external magnetic field is of crucial importance not only from a fundamental aspect, but also from a technological point of view. So far, the observations of skyrmions in bulk metallic ferromagnets have been limited to low temperatures and to materials that exhibit strong chiral interactions. In this paper, we show the formation of nanoscale skyrmions in amore » nonchiral multiferroic material, which is ferromagnetic and ferroelastic, Ni 2MnGa at room temperature without the presence of external magnetic fields. By using Lorentz transmission electron microscopy in combination with micromagnetic simulations, we elucidate their formation, behavior, and stability under applied magnetic fields at room temperature. Finally, the formation of skyrmions in a multiferroic material with no broken inversion symmetry presents new exciting opportunities for the exploration of the fundamental physics of topologically nontrivial spin textures.« less

Dehalogenation of Polybrominated Diphenyl Ethers and Polychlorinated Biphenyl by Bimetallic, Impregnated, and Nanoscale Zerovalent Iron

PubMed Central

Zhuang, Yuan; Ahn, Sungwoo; Seyfferth, Angelia L.; Masue-Slowey, Yoko; Fendorf, Scott; Luthy, Richard G.

2011-01-01

Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zero-valent, which shows the difficulty with in-situ synthesis of a significant fraction of zero-valent iron in the micro-porous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogenous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI. PMID:21557574

Exploring Iron Silicate Precursors of Ancient Iron Formations through Rock Record, Laboratory and Field Analogue Investigations

NASA Astrophysics Data System (ADS)

Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.

2016-12-01

In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican

Isolation and characterization of iron chelators from turmeric (Curcuma longa): selective metal binding by curcuminoids.

PubMed

Messner, Donald J; Surrago, Christine; Fiordalisi, Celia; Chung, Wing Yin; Kowdley, Kris V

2017-10-01

Iron overload disorders may be treated by chelation therapy. This study describes a novel method for isolating iron chelators from complex mixtures including plant extracts. We demonstrate the one-step isolation of curcuminoids from turmeric, the medicinal food spice derived from Curcuma longa. The method uses iron-nitrilotriacetic acid (NTA)-agarose, to which curcumin binds rapidly, specifically, and reversibly. Curcumin, demethoxycurcumin, and bisdemethoxycurcumin each bound iron-NTA-agarose with comparable affinities and a stoichiometry near 1. Analyses of binding efficiencies and purity demonstrated that curcuminoids comprise the primary iron binding compounds recovered from a crude turmeric extract. Competition of curcuminoid binding to the iron resin was used to characterize the metal binding site on curcumin and to detect iron binding by added chelators. Curcumin-Iron-NTA-agarose binding was inhibited by other metals with relative potency: (>90% inhibition) Cu 2+  ~ Al 3+  > Zn 2+  ≥ Ca 2+  ~ Mg 2+  ~ Mn 2+ (<20% inhibition). Binding was also inhibited by pharmaceutical iron chelators (desferoxamine or EDTA) or by higher concentrations of weak iron chelators (citrate or silibinin). Investigation of the physiological effects of iron binding by curcumin revealed that curcumin uptake by cultured cells was reduced >80% by addition of iron to the media; uptake was completely restored by desferoxamine. Ranking of metals by relative potencies for blocking curcumin uptake agreed with their relative potencies in blocking curcumin binding to iron-NTA-agarose. We conclude that curcumin can selectively bind toxic metals including iron in a physiological setting, and propose inhibition of curcumin binding to iron-NTA-agarose for iron chelator screening.

Molecular dynamics study of the interaction between nanoscale interstitial dislocation loops and grain boundaries in BCC iron

NASA Astrophysics Data System (ADS)

Gao, N.; Perez, D.; Lu, G. H.; Wang, Z. G.

2018-01-01

Atomic simulations are used to investigate the interaction between nanoscale interstitial dislocation loops and grain boundaries (GBs), the subsequent evolution of the GBs' structures, and the resulting impact on mechanical properties, in BCC iron. The interaction between loops and GBs - Σ 3 { 111 } and Σ 3 { 112 } - is affected by the angle (θ) between the Burgers vector and the normal to the GB plane, as well as by the distribution of free volume (FV) and stress. Loops can be totally absorbed by Σ 3 { 111 } boundaries, while the interaction with Σ 3 { 112 } boundaries is found to change the Burgers vector and habit plane after absorption, but to otherwise leave the loop intact, resulting in selective absorption. When θ =90o , no absorption occurs in Σ 3 { 112 } . The stress accumulation induced by the absorption affects the local mechanical properties of GBs. In nanocrystalline iron sample, a similar phenomenon is also observed, resulting in rearrangement of GBs and grain growth.

Toxic metal immobilization in contaminated sediment using bentonite- and kaolinite-supported nano zero-valent iron

NASA Astrophysics Data System (ADS)

Tomašević, D. D.; Kozma, G.; Kerkez, Dj. V.; Dalmacija, B. D.; Dalmacija, M. B.; Bečelić-Tomin, M. R.; Kukovecz, Á.; Kónya, Z.; Rončević, S.

2014-08-01

The objective of this study was to investigate the possibility of using supported nanoscale zero-valent iron with bentonite and kaolinite for immobilization of As, Pb and Zn in contaminated sediment from the Nadela river basin (Serbia). Assessment of the sediment quality based on the pseudo-total metal content (As, Pb and Zn) according to the corresponding Serbian standards shows its severe contamination, such that it requires disposal in special reservoirs and, if possible, remediation. A microwave-assisted sequential extraction procedure was employed to assess potential metal mobility and risk to the aquatic environment. According to these results, As showed lower risk to the environment than Pb and Zn, which both represent higher risk to the environment. The contaminated sediment, irrespective of the different speciation of the treated metals, was subjected to the same treatment. Semi-dynamic leaching test, based on leachability index and effective diffusion coefficients, was conducted for As-, Pb- and Zn-contaminated sediments in order to assess the long-term leaching behaviour. In order to simulate "worst case" leaching conditions, the test was modified using acetic and humic acid solution as leachants instead of deionized water. A diffusion-based model was used to elucidate the controlling leaching mechanisms; in the majority of samples, the controlling leaching mechanism appeared to be diffusion. Three different single-step leaching tests were applied to evaluate the extraction potential of examined metals. Generally, the test results indicated that the treated sediment is safe for disposal and could even be considered for "controlled utilization".

Optimization Review, Peck Iron and Metal Superfund Site, Portsmouth, Virginia

EPA Pesticide Factsheets

The Peck Iron and Metal Superfund Site is a 33-acre property located in Norfolk County, Portsmouth, Virginia. PIM (Figure 1) is the site of a former scrap metal storage and recycling facility that began operation in the 1940s.

Continuous-flow extraction system for elemental association study: a case of synthetic metal-doped iron hydroxide.

PubMed

Hinsin, Duangduean; Pdungsap, Laddawan; Shiowatana, Juwadee

2002-12-06

A continuous-flow extraction system originally developed for sequential extraction was applied to study elemental association of a synthetic metal-doped amorphous iron hydroxide phase. The homogeneity and metal association of the precipitates were evaluated by gradual leaching using the system. Leachate was collected in fractions for determination of elemental concentrations. The result obtained as extractograms indicated that the doped metals were adsorbed more on the outermost surface rather than homogeneously distributed in the precipitates. The continuous-flow extraction method was also used for effective removal of surface adsorbed metals to obtain a homogeneous metal-doped synthetic iron hydroxide by a sequential extraction using acetic acid and small volume of hydroxylamine hydrochloride solution. The system not only ensures complete washing, but the extent of metal immobilization in the synthetic iron hydroxide could be determined with high accuracy from the extractograms. The initial metal/iron mole ratio (M/Fe) in solution affected the M/Fe mole ratio in homogeneous doped iron hydroxide phase. The M/Fe mole ratio of metal incorporation was approximately 0.01-0.02 and 0.03-0.06, for initial solution M/Fe mole ratio of 0.025 and 0.100, respectively.

Rapid reductive degradation of aqueous p-nitrophenol using nanoscale zero-valent iron particles immobilized on mesoporous silica with enhanced antioxidation effect

NASA Astrophysics Data System (ADS)

Tang, Lin; Tang, Jing; Zeng, Guangming; Yang, Guide; Xie, Xia; Zhou, Yaoyu; Pang, Ya; Fang, Yan; Wang, Jiajia; Xiong, Weiping

2015-04-01

In this study, nanoscale zero-valent iron particles immobilized on mesoporous silica (nZVI/SBA-15) were successfully prepared for effective degradation of p-nitrophenol (PNP). The nZVI/SBA-15 composites were characterized by N2 adsorption/desorption, transmission electron microscopy (TEM), UV-vis spectrum and X-ray photoelectron spectroscopy (XPS). Results showed that abundant ultrasmall nanoscale zero-valent iron particles were formed and well dispersed on mesoporous silica (SBA-15). Batch experiments revealed that PNP removal declined from 96.70% to 16.14% as solution pH increased from 3.0 to 9.0. Besides, degradation equilibrium was reached within 5 min, which was independent of initial PNP concentration. Furthermore, only a little PNP elimination on SBA-15 indicated that nZVI immobilized on mesoporous silica was mainly responsible for the target contaminant removal. The UV-vis spectrum and XPS measurement confirmed that the PNP removal was a reductive degradation process, which was further proved by the detected intermediates using gas chromatography-mass spectrometry (GC/MS). The excellent antioxidation ability had been discovered with more than 80% of PNP being removed by nZVI/SBA-15 treated with 30 days' exposure to air. These results demonstrated the feasible and potential application of nZVI/SBA-15 composites in organic wastewater treatment.

Nanoscale zerovalent iron (nZVI) supported by natural and acid-activated sepiolites: the effect of the nZVI/support ratio on the composite properties and Cd2+ adsorption.

PubMed

Habish, Amal Juma; Lazarević, Slavica; Janković-Častvan, Ivona; Jokić, Bojan; Kovač, Janez; Rogan, Jelena; Janaćković, Đorđe; Petrović, Rada

2017-01-01

Natural (SEP) and partially acid-activated (AAS) sepiolites were used to prepare composites with nanoscale zerovalent iron (nZVI) at different (SEP or AAS)/nZVI ratios in order to achieve the best nZVI dispersibility and the highest adsorption capacity for Cd 2+ . Despite the higher surface area and pore volume of AAS, better nZVI dispersibility was achieved by using SEP as the support. On the other hand, a lower oxidation degree was achieved during the synthesis using AAS. X-ray photoelectron spectroscopy (XPS) analysis of the composite with the best nZVI dispersibility, before and after Cd 2+ adsorption, confirmed that the surface of the nZVI was composed of oxidized iron species. Metallic iron was not present on the surface, but it was detected in the subsurface region after sputtering. The content of zerovalent iron decreased after Cd 2+ adsorption as a result of iron oxidation during Cd 2+ adsorption. The XPS depth profile showed that cadmium was present not only at the surface of the composite but also in the subsurface region. The adsorption isotherms for Cd 2+ confirmed that the presence of SEP and AAS decreased the agglomeration of the nZVI particles in comparison to the pure nZVI, which provided a higher adsorption capacity. The results showed that the prevention of both aggregation and oxidation during the synthesis was necessary for obtaining an SEP/AAS-nZVI composite with a high adsorption capacity, but oxidation during adsorption was beneficial for Cd 2+ removal. The formation of strong bonds between Cd 2+ and the adsorbents sites of different energy until monolayer formation was proposed according to modeling of the adsorption isotherms.

Emulsified Zero-Valent Nano-Scale Iron Treatment of Chlorinated Solvent DNAPL Source Areas

DTIC Science & Technology

2010-09-01

Significant laboratory and field research has demonstrated that zero-valent metals will reductively dehalogenate dissolved chlorinated solvents such as...Eekert, Servé W. M. Kengen, Gosse Schraa, and Alfons J. M. Stams. 1999. Anaerobic Microbial Reductive Dehalogenation of Chlorinated Ethenes...and T. Holdsworth. 2005. Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron. Environmental Science Technology, vol 39

Mixed-valent dicobalt and iron-cobalt complexes with high-spin configurations and short metal-metal bonds.

PubMed

Zall, Christopher M; Clouston, Laura J; Young, Victor G; Ding, Keying; Kim, Hyun Jung; Zherebetskyy, Danylo; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

2013-08-19

Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.

Ionic liquid-based extraction followed by graphite-furnace atomic absorption spectrometry for the determination of trace heavy metals in high-purity iron metal.

PubMed

Matsumiya, Hiroaki; Kato, Tatsuya; Hiraide, Masataka

2014-02-01

The analysis of high-purity materials for trace impurities is an important and challenging task. The present paper describes a facile and sensitive method for the determination of trace heavy metals in high-purity iron metal. Trace heavy metals in an iron sample solution were rapidly and selectively preconcentrated by the extraction into a tiny volume of an ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] for the determination by graphite-furnace atomic absorption spectrometry (GFAAS). A nitrogen-donating neutral ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), was found to be effective in the ionic liquid-based selective extraction, allowing the nearly complete (~99.8%) elimination of the iron matrix. The combination with the optimized GFAAS was successful. The detectability reached sub-μg g(-1) levels in iron metal. The novel use of TPTZ in ionic liquid-based extraction followed by GFAAS was successfully applied to the determination of traces of Co, Ni, Cu, Cd, and Pb in certified reference materials for high-purity iron metal. © 2013 Published by Elsevier B.V.

Multiscale correlations of iron phases and heavy metals in technogenic magnetic particles from contaminated soils.

PubMed

Yu, Xiuling; Lu, Shenggao

2016-12-01

Technogenic magnetic particles (TMPs) are carriers of heavy metals and organic contaminants, which derived from anthropogenic activities. However, little information on the relationship between heavy metals and TMP carrier phases at the micrometer scale is available. This study determined the distribution and association of heavy metals and magnetic phases in TMPs in three contaminated soils at the micrometer scale using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy. Multiscale correlations of heavy metals in TMPs were elucidated using wavelet transform analysis. μ-XRF mapping showed that Fe was enriched and closely correlated with Co, Cr, and Pb in TMPs from steel industrial areas. Fluorescence mapping and wavelet analysis showed that ferroalloy was a major magnetic signature and heavy metal carrier in TMPs, because most heavy metals were highly associated with ferroalloy at all size scales. Multiscale analysis revealed that heavy metals in the TMPs were from multiple sources. Iron K-edge μ-XANES spectra revealed that metallic iron, ferroalloy, and magnetite were the main iron magnetic phases in the TMPs. The relative percentage of these magnetic phases depended on their emission sources. Heatmap analysis revealed that Co, Pb, Cu, Cr, and Ni were mainly derived from ferroalloy particles, while As was derived from both ferroalloy and metallic iron phases. Our results indicated the scale-dependent correlations of magnetic phases and heavy metals in TMPs. The combination of synchrotron based X-ray microprobe techniques and multiscale analysis provides a powerful tool for identifying the magnetic phases from different sources and quantifying the association of iron phases and heavy metals at micrometer scale. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transformation and composition evolution of nanoscale zero valent iron (nZVI) synthesized by borohydride reduction in static water.

PubMed

Liu, Airong; Liu, Jing; Zhang, Wei-Xian

2015-01-01

The reactivity of nanoscale zero valent iron (nZVI) toward targeted contaminants is affected by the initial nZVI composition and the iron oxides formed during the aging process in aquatic systems. In this paper, the aging effects of nZVI, prepared using a borohydride reduction method in static water over a period of 90 days (d), are investigated. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy are used to characterize the corrosion products of nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging. The products of nZVI aged for 5 d in static water media are mainly magnetite (Fe3O4) and maghemite (γ-Fe2O3), accompanied by lepidocrocite (γ-FeOOH). For products aged 10 d, XRD data show the formation of ferrihydrite and lepidocrocite. When aged up to 90 d, the products are mainly γ-FeOOH mixed with small amounts of Fe3O4 and γ-Fe2O3. Transmission electronic microscopy (TEM) images show that the core-shell structure forms into a hollow spherical shape after 30 d of aging in aquatic media. The results indicate first that iron ions in the Fe(0) core diffuse outwardly toward the shell, and hollowed-out iron oxide shells emerge. Then, the iron oxide shell collapses and becomes a flaky, acicular-shaped structure. The type and the crystal phase of second iron oxide minerals are vastly different at various aging times. This study helps to explain the patterns of occurrence of specific iron oxides in different natural conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Manipulating Energy Flow at the Nanoscale by Coupling Plasmons of Metal Nanostructures to Resonant Molecules

NASA Astrophysics Data System (ADS)

Wiederrecht, Gary

2014-03-01

Collective hybrid excitations resulting from the coupling of metal nanostructures with organic molecules present unique opportunities for manipulating light-matter interactions at the nanoscale. In this talk, I discuss recent studies that are examples of the breadth of phenomena that are possible. First, the interactions of coupled plasmonic nanostructures with azobenzene-based polymers are described, in which the spatial features of the plasmonic near-field can be used to manipulate molecular motion. The directional molecular transport that results is shown to be useful for imaging the spatial and polarization features of the optical near-field. The modeling of this effect is described. Second, the coupling of excitonic molecular aggregates to metal nanostructures produces coherent coupling that provides added structure to the optical extinction spectra of metal nanoparticles, thereby by providing a photonic handle with which to manipulate energy flow on an ultrafast timescale. Monitoring the rate of energy flow as a function of photon energy reveals important information about the energy dissipation channels and the structural interactions between molecule and metal. Third, the strongly enhanced optical nonlinearity resulting from coupled plasmonic nanorods is described. The closely spaced nanorod material exhibits nonlocality of the optical response that has an unusually strong nonlinear dependence on incident light intensity. Electromagnetic modeling confirms the nonlocal response of the plasmonic metamaterial. The broader impact of collective hybrid excitations on nanophotonics applications is described. Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-06CH11357.

Magnetic iron oxides in the cementation technology of the boron-containing radioactive waste

NASA Astrophysics Data System (ADS)

Fedotov, M. A.; Gorbunova, O. A.; Fedorova, O. V.; Folmanis, G. E.; Kovalenko, L. V.

2015-04-01

Two ways of synthesis of non-detachable dispersed particles of magnetic materials useful for the boron-containing waste cementation process regulation were developed. Powder XRD showed that the method of carbothermic recovery of nanoscale iron hydroxide allows obtaining a mixture of iron oxides with content of the magnetic phase up to 70%. Method of low-temperature hydrogen reduction of the raw materials allows obtaining various compositions of a-iron and iron oxides with the possibility to change the size of the final particles in a wide range. The possibility of using composites of magnetic iron oxides and metal oxide compositions instead of ferromagnetic rods with VEP of boron-containing liquid radioactive waste in the fluidized field was studied. It was shown that the use of fine and nano particles of the iron oxides in the pre-treatment of the boron-containing LRW increases the strength of the final compounds and accelerates the cement setting compounds from 13 to 5-9 days.

The removal of lead and nickel from the composted municipal waste and sewage sludge using nanoscale zero-valent iron fixed on quartz.

PubMed

Ghasemzadeh, Parisa; Bostani, Amir

2017-11-01

Reducing the concentration of heavy metals including lead (Pb) and nickel (Ni) in organic contaminants such as municipal wastes and sewage sludge is of health and environmental importance. Nanoscale zero-valent iron (NZVI) particles can effectively remove heavy metals from contaminated aqueous and solid media. It was accordingly hypothesized that it is possible to recycle and detoxify organic waste materials containing heavy metals using NZVI and NZVI fixed on quartz (QNZVI). The objective was to investigate the effects of NZVI type, concentration (2% and 5%) and contact time on the removal of Pb and Ni from raw compost, compost fermented with beet molasses, and leachate using a factorial design. The results indicated the significant reduction of DTPA- Pb and DTPA-Ni concentration, in all the organic compounds treated with NZVI and QNZVI (P= 0.01), compared with control. Increased concentration of NZVI in all treatments, increased the rate of DTPA-Pb and DTPA-Ni (P= 0.01) at 113.1% and 180% for Pb (NZVI at 2% and 5%), and at 16.3% and 23.3% for Ni, irrespective of the NZVI type. The reducing trend of extractable Pb and Ni in all the organic compounds was the same, quick reduction at the beginning, followed by a negligible rate. The highest reduction rates for Pb (at one hour) and Ni (at 672h) were equal to 72.93% and 23.27%, respectively. NZVI at 2% was more efficient than NZVI at 5%. There were not any significant differences between NZVI and QNZVI on the removal of Pb and Ni from the organic contaminants. It is possible to immobilize and reduce the concentration of heavy metals such as Pb and Ni in organic contaminants using NZVI, which is affected by NZVI properties, concentration, and contact time, as well as by organic contaminant type. Copyright © 2017 Elsevier Inc. All rights reserved.

Nanoscale doping heterogeneity in few-layer WSe2 exfoliated onto noble metals revealed by correlated SPM and TERS imaging

NASA Astrophysics Data System (ADS)

Jariwala, Deep; Krayev, Andrey; Wong, Joeson; Robinson, A. Edward; Sherrott, Michelle C.; Wang, Shuo; Liu, Gang-Yu; Terrones, Mauricio; Atwater, Harry A.

2018-07-01

While extensive research effort has been devoted to the study of the 2D semiconductor–insulator interfaces in transition metal dichalcogenides (TMDCs), there is little knowledge about the electronic quality of the semiconductor–metal interface in the atomically thin limit. Here, we present the first correlated nanoscale mapping of the interface of atomically thin WSe2 with noble metals using co-localized scanning probe microscopy and tip-enhanced optical spectroscopy (TEOS), such as tip-enhanced Raman spectroscopy (TERS). Nanoscale maps of the topography, surface potential, Raman spectra, and the photocurrent amplitude of the WSe2/metal interfaces reveal striking results. Specifically, correlations between surface potential, resonant Raman signatures and photocurrents that indicate the presence of inhomogeneities within interfacial electronic properties, which we attribute to variations in the local doping of the WSe2 likely caused by intrinsic compositional fluctuations or defects. Our results suggest that local electrostatic variations at a lateral scale of 10–100 nm are present even in the highest quality of TMDC crystals and must be considered towards understanding of all interfacial phenomena, particularly in device applications that rely on the buried metal–semiconductor junction interface.

FORMATION MECHANISM FOR THE NANOSCALE AMORPHOUS INTERFACE IN PULSE-WELDED AL/FE BIMETALLIC SYSTEM

DOE PAGES

Li, Jingjing; Yu, Qian; Zhang, Zijiao; ...

2016-05-20

Pulse or impact welding traditionally has been referred to as “solid-state” welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed inmore » the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the resulted recrystallization occurred on the aluminum side of the interface.« less

FORMATION MECHANISM FOR THE NANOSCALE AMORPHOUS INTERFACE IN PULSE-WELDED AL/FE BIMETALLIC SYSTEM

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

Li, Jingjing; Yu, Qian; Zhang, Zijiao

Pulse or impact welding traditionally has been referred to as “solid-state” welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed inmore » the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the resulted recrystallization occurred on the aluminum side of the interface.« less

Formation mechanism for the nanoscale amorphous interface in pulse-welded Al/Fe bimetallic systems

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

Li, Jingjing; Yu, Qian; Zhang, Zijiao

Pulse or impact welding traditionally has been referred to as “solid-state” welding. By integrating advanced interface characterizations and diffusion calculations, we report that the nanoscale amorphous interface in the pulse-welded Al/Fe bimetallic system is formed by rapid heating and melting of a thin Al layer at the interface, diffusion of iron atoms in the liquid aluminum, and subsequent rapid quenching with diffused iron atoms in solution. This finding challenges the commonly held belief regarding the solid-state nature of the impact-based welding process for dissimilar metals. Elongated ultra-fine grains with high dislocation density and ultra-fine equiaxed grains also are observed inmore » the weld interface vicinity on the steel and aluminum sides, respectively, which further confirms that melting and the subsequent recrystallization occurred on the aluminum side of the interface.« less

Synchrotron speciation data for zero-valent iron nanoparticles

EPA Pesticide Factsheets

This data set encompasses a complete analysis of synchrotron speciation data for 5 iron nanoparticle samples (P1, P2, P3, S1, S2, and metallic iron) to include linear combination fitting results (Table 6 and Figure 9) and ab-initio extended x-ray absorption fine structure spectroscopy fitting (Figure 10 and Table 7).Table 6: Linear combination fitting of the XAS data for the 5 commercial nZVI/ZVI products tested. Species proportions are presented as percentages. Goodness of fit is indicated by the chi^2 value.Figure 9: Normalised Fe K-edge k3-weighted EXAFS of the 5 commercial nZVI/ZVIproducts tested. Dotted lines show the best 4-component linear combination fit ofreference spectra.Figure 10: Fourier transformed radial distribution functions (RDFs) of the five samplesand an iron metal foil. The black lines in Fig. 10 represent the sample data and the reddotted curves represent the non-linear fitting results of the EXAFS data.Table 7: Coordination parameters of Fe in the samples.This dataset is associated with the following publication:Chekli, L., B. Bayatsarmadi, R. Sekine, B. Sarkar, A. Maoz Shen, K. Scheckel , W. Skinner, R. Naidu, H. Shon, E. Lombi, and E. Donner. Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review. Richard P. Baldwin ANALYTICA CHIMICA ACTA. Elsevier Science Ltd, New York, NY, USA, 903: 13-35, (2016).

Thermal Conductivity of a Nanoscale Yttrium Iron Garnet Thin-Film Prepared by the Sol-Gel Process

PubMed Central

2017-01-01

The thermal conductivity of a nanoscale yttrium iron garnet (Y3Fe5O12, YIG) thin-film prepared by a sol-gel method was evaluated using the ultrafast pump-probe technique in the present study. The thermoreflectance change on the surface of a 250 nm thick YIG film, induced by the irradiation of femtosecond laser pulses, was measured, and curve fitting of a numerical solution for the transient heat conduction equation to the experimental data was performed using the finite difference method in order to extract the thermal property. Results show that the film’s thermal conductivity is 22–83% higher than the properties of bulk YIG materials prepared by different fabrication techniques, reflecting the microstructural characteristics and quality of the film. PMID:28858249

Fabrication of Nanoscale Circuits on Inkjet-Printing Patterned Substrates.

PubMed

Chen, Shuoran; Su, Meng; Zhang, Cong; Gao, Meng; Bao, Bin; Yang, Qiang; Su, Bin; Song, Yanlin

2015-07-08

Nanoscale circuits are fabricated by assembling different conducting materials (e.g., metal nanoparticles, metal nano-wires, graphene, carbon nanotubes, and conducting polymers) on inkjet-printing patterned substrates. This non-litho-graphy strategy opens a new avenue for integrating conducting building blocks into nanoscale devices in a cost-efficient manner. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

NASA Technical Reports Server (NTRS)

Jurewicz, Stephen R.; Jones, J. H.

1993-01-01

Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

Atomistic Design and Simulations of Nanoscale Machines and Assembly

NASA Technical Reports Server (NTRS)

Goddard, William A., III; Cagin, Tahir; Walch, Stephen P.

2000-01-01

Over the three years of this project, we made significant progress on critical theoretical and computational issues in nanoscale science and technology, particularly in:(1) Fullerenes and nanotubes, (2) Characterization of surfaces of diamond and silicon for NEMS applications, (3) Nanoscale machine and assemblies, (4) Organic nanostructures and dendrimers, (5) Nanoscale confinement and nanotribology, (6) Dynamic response of nanoscale structures nanowires (metals, tubes, fullerenes), (7) Thermal transport in nanostructures.

Performance Optimization of Metallic Iron and Iron Oxide Nanomaterials for Treatment of Impaired Water Supplies

NASA Astrophysics Data System (ADS)

Xie, Yang

Iron nanomaterials including nanoscale zero valent iron (NZVI), NZVI-based bimetallic reductants (e.g., Pd/NZVI) and naturally occurring nanoscale iron mineral phases represent promising treatment tools for impaired water supplies. However, questions pertaining to fundamental and practical aspects of their reactivity may limit their performance during applications. For NZVI treatment of pollutant source zones, a major hurdle is its limited reactive lifetime. In Chapter 2, we report the longevity of NZVI towards 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and hexavalent chromium [Cr(VI)] in oxygen-free systems with various anionic co-solutes (e.g., Cl-, SO4 2-, ClO4-, HCO3 -, NO3-). Trends in longevity provide evidence that surface-associated Fe(II) species are responsible for Cr(VI) reduction, whereas 1,1,1,2-TeCA reduction depends on the accessibility of Fe(0) at the NZVI particle surface. In Chapter 3, we show that dithionite, previously utilized for in situ redox manipulation, can restore the reducing capacity of passivated NZVI treatment systems. Air oxidation of NZVI at pH ≥ 8 quickly exhausted reactivity despite a significant fraction of Fe(0) persisting in the particle core. Reduction of this passive layer by low dithionite concentrations restored suspension reactivity to levels of unaged NZVI, with multiple dithionite additions further improving pollutant removal. In Chapter 4, measurements of solvent kinetic isotope effects reveals that optimal Pd/NZVI reactivity results from accumulation of atomic hydrogen, which only occurs in NZVI-based systems due to their higher rates of corrosion. However, atomic hydrogen formation only occurs in aged Pd/NZVI suspensions for ˜2 weeks, after which any reactivity enhancement likely results from galvanic corrosion of Fe(0). Finally, the activity of hybrid nanostructures consisting of multi-walled carbon nanotubes decorated with of hematite nanoparticles (alphaFe 2O3/MWCNT) is explored in Chapter 5. Sorption of Cu

Bioaccessibility of micron-sized powder particles of molybdenum metal, iron metal, molybdenum oxides and ferromolybdenum--Importance of surface oxides.

PubMed

Mörsdorf, Alexander; Odnevall Wallinder, Inger; Hedberg, Yolanda

2015-08-01

The European chemical framework REACH requires that hazards and risks posed by chemicals, including alloys and metals, that are manufactured, imported or used in different products (substances or articles) are identified and proven safe for humans and the environment. Metals and alloys need hence to be investigated on their extent of released metals (bioaccessibility) in biologically relevant environments. Read-across from available studies may be used for similar materials. This study investigates the release of molybdenum and iron from powder particles of molybdenum metal (Mo), a ferromolybdenum alloy (FeMo), an iron metal powder (Fe), MoO2, and MoO3 in different synthetic body fluids of pH ranging from 1.5 to 7.4 and of different composition. Spectroscopic tools and cyclic voltammetry have been employed to characterize surface oxides, microscopy, light scattering and nitrogen absorption for particle characterization, and atomic absorption spectroscopy to quantify released amounts of metals. The release of molybdenum from the Mo powder generally increased with pH and was influenced by the fluid composition. The mixed iron and molybdenum surface oxide of the FeMo powder acted as a barrier both at acidic and weakly alkaline conditions. These findings underline the importance of the surface oxide characteristics for the bioaccessibility of metal alloys. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Formation of iron metal and grain coagulation in the solar nebula

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Berg, Otto

1994-01-01

The interstellar grain population in the giant molecular cloud from which the sun formed contained little or no iron metal. However, thermal processing of individual interstellar silicates in the solar nebula is likely to result in the formation of a population of very small iron metal grains. If such grains are exposed to even transient magnetic fields, each will become a tiny dipole magnet capable of interacting with other such dipoles over spatial scale orders of magnitude larger than the radii of individual grains. Such interactions will greatly increase the coagulation cross-section for this grain population. Furthermore, the magnetic attraction between two iron dipoles will significantly increase both the collisional sticking coefficient and the strength of the interparticle binding energy for iron aggregates. Formation of iron metal may therefore be a key step in the aggregation of planetesimals in a protoplanetary nebula. Such aggregates may have already been observed in protoplanetary systems. The enhancement in the effective interaction distance between two magnetic dipoles is directly proportional to the strength of the magnetic dipoles and inversely proportional to the relative velocity. It is less sensitive to the reduced mass of the interacting particles (alpha M(exp -1/2)) and almost insensitive to the initial number density of magnetic dipoles (alpha n(sub o)(exp 1/6)). We are in the process of measuring the degree of coagulation in our condensation flow apparatus as a function of applied magnetic field and correlating these results by means of magnetic remanance acquisition measurements on our iron grains with the strength of the magnetic field to which the grains are exposed. Results of our magnetic remanance acquisition measurements and the magnetic-induced coagulation study will be presented as well as an estimate of the importance of such processes near the nebular midplane.

Recyclable nanoscale zero-valent iron-based magnetic polydopamine coated nanomaterials for the adsorption and removal of phenanthrene and anthracene

PubMed Central

Li, Jing; Zhou, Qingxiang; Liu, Yongli; Lei, Man

2017-01-01

Abstract In this study, nanoscale zero-valent iron nanoparticles (NZVIs) were coated with silica and polydopamine using a two-step process. The coated nanoparticles were applied as adsorbents for removal of two common polycyclic aromatic hydrocarbons pollutants, phenanthrene (PHE) and anthracene (ANT) from aqueous system. Adsorption kinetics followed a pseudo-second-order model. Isotherms and thermodynamics were investigated and the results indicated that the adsorption process fit best to the Freundlich model and exhibited the characteristics of an exothermal physical adsorption process. Owing to their superparamagnetic characteristics and stability, these adsorbents could be easily collected and recycled for reuse. PMID:28179954

Recyclable nanoscale zero-valent iron-based magnetic polydopamine coated nanomaterials for the adsorption and removal of phenanthrene and anthracene

NASA Astrophysics Data System (ADS)

Li, Jing; Zhou, Qingxiang; Liu, Yongli; Lei, Man

2017-12-01

In this study, nanoscale zero-valent iron nanoparticles (NZVIs) were coated with silica and polydopamine using a two-step process. The coated nanoparticles were applied as adsorbents for removal of two common polycyclic aromatic hydrocarbons pollutants, phenanthrene (PHE) and anthracene (ANT) from aqueous system. Adsorption kinetics followed a pseudo-second-order model. Isotherms and thermodynamics were investigated and the results indicated that the adsorption process fit best to the Freundlich model and exhibited the characteristics of an exothermal physical adsorption process. Owing to their superparamagnetic characteristics and stability, these adsorbents could be easily collected and recycled for reuse.

Effect of anions and humic acid on the performance of nanoscale zero-valent iron particles coated with polyacrylic acid.

PubMed

Kim, Hong-Seok; Ahn, Jun-Young; Kim, Cheolyong; Lee, Seockheon; Hwang, Inseong

2014-10-01

Effects of anions (NO3(-), HCO3(-), Cl(-), SO4(2-)) and humic acid on the reactivity and core/shell chemistries of polyacrylic acid-coated nanoscale zero-valent iron (PAA-NZVI) and inorganically modified NZVI (INORG-NZVI) particles were investigated. The reactivity tests under various ion concentrations (0.2-30mN) revealed the existence of a favorable molar ratio of anion/NZVI that increased the reactivity of NZVI particles. The presence of a relatively small amount of humic acid (0.5mgL(-1)) substantially decreased the INORG-NZVI reactivity by 76%, whereas the reactivity of PAA-NZVI decreased only by 12%. The XRD and TEM results supported the role of the PAA coating of PAA-NZVI in impeding the oxidation of the Fe(0) core by groundwater solutes. This protective role provided by the organic coating also resulted in a 2.3-fold increase in the trichloroethylene (TCE) reduction capacity of PAA-NZVI compared to that of INORG-NZVI in the presence of anions/humic acid. Ethylene and ethane were simultaneously produced as the major reduction products of TCE in both NZVI systems, suggesting that a hydrodechlorination occurred without the aid of metallic catalysts. The PAA coating, originally designed to improve the mobility of NZVI, enhanced TCE degradation performances of NZVI in the presence of anions and humic acid. Copyright © 2014 Elsevier Ltd. All rights reserved.

Micro-electrolysis of Cr (VI) in the nanoscale zero-valent iron loaded activated carbon.

PubMed

Wu, Limei; Liao, Libing; Lv, Guocheng; Qin, Faxiang; He, Yujuan; Wang, Xiaoyu

2013-06-15

In this paper we prepared a novel material of activated carbon/nanoscale zero-valent iron (C-Fe(0)) composite. The C-Fe(0) was proved to possess large specific surface area and outstanding reducibility that result in the rapid and stable reaction with Cr (VI). The prepared composite has been examined in detail in terms of the influence of solution pH, concentration and reaction time in the Cr (VI) removal experiments. The results showed that the C-Fe(0) formed a micro-electrolysis which dominated the reaction rate. The Micro-electrolysis reaches equilibrium is ten minutes. Its reaction rate is ten times higher than that of traditional adsorption reaction, and the removal rate of Cr reaches up to 99.5%. By analyzing the obtained profiles from the cyclic voltammetry, PXRD and XPS, we demonstrate that the Cr (VI) is reduced to insoluble Cr (III) compound in the reaction. Copyright © 2013 Elsevier B.V. All rights reserved.

Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene.

PubMed

Yan, Jingchun; Han, Lu; Gao, Weiguo; Xue, Song; Chen, Mengfang

2015-01-01

Biochar (BC) supported nanoscale zerovalent iron (nZVI) composite was synthesized and used as an activator for persulfate to enhance the trichloroethylene (TCE) removal in aqueous solutions. The degradation efficiency of TCE (0.15mmolL(-1)) was 99.4% in the presence of nZVI/BC (4.5mmolL(-1), nZVI to BC mass ratio was 1:5) and persulfate (4.5mmolL(-1)) within 5min, which was significantly higher than that (56.6%) in nZVI-persulfate system under the same conditions. Owing to large specific surface area and oxygen-containing functional groups of BC, nZVI/BC enhanced the SO4(-) generation and accelerated TCE degradation. On the basis of the characterization and analysis data, possible activation mechanisms of the Fe(2+)/Fe(3+) (Fe(II)/Fe(III)) redox action and the electron-transfer mediator of the BC oxygen functional groups promoting the generation of SO4(-) in nZVI/BC-persulfate system were clarified. Copyright © 2014 Elsevier Ltd. All rights reserved.

The mechanical behavior of nanoscale metallic multilayers: A survey

NASA Astrophysics Data System (ADS)

Zhou, Q.; Xie, J. Y.; Wang, F.; Huang, P.; Xu, K. W.; Lu, T. J.

2015-06-01

The mechanical behavior of nanoscale metallic multilayers (NMMs) has attracted much attention from both scientific and practical views. Compared with their monolithic counterparts, the large number of interfaces existing in the NMMs dictates the unique behavior of this special class of structural composite materials. While there have been a number of reviews on the mechanical mechanism of microlaminates, the rapid development of nanotechnology brought a pressing need for an overview focusing exclusively on a property-based definition of the NMMs, especially their size-dependent microstructure and mechanical performance. This article attempts to provide a comprehensive and up-to-date review on the microstructure, mechanical property and plastic deformation physics of NMMs. We hope this review could accomplish two purposes: (1) introducing the basic concepts of scaling and dimensional analysis to scientists and engineers working on NMM systems, and (2) providing a better understanding of interface behavior and the exceptional qualities the interfaces in NMMs display at atomic scale.

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: the role of Fe(II) and Fe(III).

PubMed

Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

2014-12-01

The role of Fe(II) and Fe(III) in U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed that U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.9 to 9.0. For instance, at pH 6.9 the observed U(VI) reduction rates decreased by 81% and 82% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) possibly acted as an electron shuttle to ferry the electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 could facilitate U(VI) reductive immobilization in the contaminated groundwater.

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

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

Yan, Sen; Chen, Yongheng; Xiang, Wu

2014-12-01

The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can bemore » enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.« less

UPTAKE OF HEAVY METALS IN BATCH SYSTEMS BY A RECYCLED IRON-BEARING MATERIAL

EPA Science Inventory

An iron-bearing material deriving from surface finishing operations in the manufacturing of cast-iron components demonstrates potential for removal of heavy metals from aqueous waste streams. Batch isotherm and rate experiments were conducted for uptake of cadmium, zinc, and lead...

Removal of water contaminants by nanoscale zero-valent iron immobilized in PAN-based oxidized membrane

NASA Astrophysics Data System (ADS)

Liu, Chunyi; Li, Xiang; Ma, Bomou; Qin, Aiwen; He, Chunju

2014-12-01

The functionalizing nanoporous polyacrylonitrile-based oxidized membrane (PAN-OM) firmly immobilized with highly reactive nanoscale zero-valent iron (NZVI) are successfully prepared via an innovative in situ synthesis method. Due to the formation of ladder structure, the PAN-OM present excellent thermal and chemical stabilities as a new carrier for the in-situ growth of NZVI via firm chelation and reduction action, respectively, which prevent the aggregation and release of NZVI. The developed NZVI-immobilized membrane present effective decolorizing efficiency to both anionic methyl blue and cationic methylene blue with a pseudo-first-order decay and degrading efficiency to trichloroethylene (TCE). The regeneration and stability results show that NZVI-immobilized membrane system can be regenerated without obvious performance reduction, which remain the reactivity after half a year storage period. These results suggest that PAN-based oxidized membrane immobilized with NZVI exhibit significant potential for environmental applications.

Ochrobactrum anthropi used to control ammonium for nitrate removal by starch-stabilized nanoscale zero valent iron.

PubMed

Zhou, Jun; Sun, Qianyu; Chen, Dan; Wang, Hongyu; Yang, Kai

2017-10-01

In this study, the hydrogenotrophic denitrifying bacterium Ochrobactrum anthropi was added in to the process of nitrate removal by starch-stabilized nanoscale zero valent iron (nZVI) to minimize undesirable ammonium. The ammonium control performance and cooperative mechanism of this combined process were investigated, and batch experiments were conducted to discuss the effects of starch-stabilized nZVI dose, biomass, and pH on nitrate reduction and ammonium control of this system. The combined system achieved satisfactory performance because the anaerobic iron corrosion process generates H 2 , which is used as an electron donor for the autohydrogenotrophic bacterium Ochrobactrum anthropi to achieve the autohydrogenotrophic denitrification process converting nitrate to N 2 . When starch-stabilized nZVI dose was increased from 0.5 to 2.0 g/L, nitrate reduction rate gradually increased, and ammonium yield also increased from 9.40 to 60.51 mg/L. Nitrate removal rate gradually decreased and ammonium yield decreased from 14.93 to 2.61 mg/L with initial OD 600 increasing from 0.015 to 0.080. The abiotic Fe 0 reduction process played a key role in nitrate removal in an acidic environment and generated large amounts of ammonium. Meanwhile, the nitrate removal rate decreased and ammonium yield also reduced in an alkaline environment.

Coherent Control of Nanoscale Ballistic Currents in Transition Metal Dichalcogenide ReS2.

PubMed

Cui, Qiannan; Zhao, Hui

2015-04-28

Transition metal dichalcogenides are predicted to outperform traditional semiconductors in ballistic devices with nanoscale channel lengths. So far, experimental studies on charge transport in transition metal dichalcogenides are limited to the diffusive regime. Here we show, using ReS2 as an example, all-optical injection, detection, and coherent control of ballistic currents. By utilizing quantum interference between one-photon and two-photon interband transition pathways, ballistic currents are injected in ReS2 thin film samples by a pair of femtosecond laser pulses. We find that the current decays on an ultrafast time scale, resulting in an electron transport of only a fraction of one nanometer. Following the relaxation of the initially injected momentum, backward motion of the electrons for about 1 ps is observed, driven by the Coulomb force from the oppositely moved holes. We also show that the injected current can be controlled by the phase of the laser pulses. These results demonstrate a new platform to study ballistic transport of nonequilibrium carriers in transition metal dichalcogenides.

Ultrasmall water-soluble metal-iron oxide nanoparticles as T1-weighted contrast agents for magnetic resonance imaging.

PubMed

Zeng, Leyong; Ren, Wenzhi; Zheng, Jianjun; Cui, Ping; Wu, Aiguo

2012-02-28

Using an improved hydrolysis method of inorganic salts assisted with water-bath incubation, ultrasmall water-soluble metal-iron oxide nanoparticles (including Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles) were synthesized in aqueous solutions, which were used as T(1)-weighted contrast agents for magnetic resonance imaging (MRI). The morphology, structure, MRI relaxation properties and cytotoxicity of the as-prepared metal-iron oxide nanoparticles were characterized, respectively. The results showed that the average sizes of nanoparticles were about 4 nm, 4 nm and 5 nm for Fe(3)O(4), ZnFe(2)O(4) and NiFe(2)O(4) nanoparticles, respectively. Moreover, the nanoparticles have good water dispersibility and low cytotoxicity. The MRI test showed the strong T(1)-weighted, but the weak T(2)-weighted MRI performance of metal-iron oxide nanoparticles. The high T(1)-weighted MRI performance can be attributed to the ultrasmall size of metal-iron oxide nanoparticles. Therefore, the as-prepared metal-iron oxide nanoparticles with good water dispersibility and ultrasmall size can have potential applications as T(1)-weighted contrast agent materials for MRI.

Electron Beam-Induced Writing of Nanoscale Iron Wires on a Functional Metal Oxide

PubMed Central

2013-01-01

Electron beam-induced surface activation (EBISA) has been used to grow wires of iron on rutile TiO2(110)-(1 × 1) in ultrahigh vacuum. The wires have a width down to ∼20 nm and hence have potential utility as interconnects on this dielectric substrate. Wire formation was achieved using an electron beam from a scanning electron microscope to activate the surface, which was subsequently exposed to Fe(CO)5. On the basis of scanning tunneling microscopy and Auger electron spectroscopy measurements, the activation mechanism involves electron beam-induced surface reduction and restructuring. PMID:24159366

Metallic Iron and Iron Oxide as an Explanation for the Dark Material Observed on Saturn's Icy Satellites and Rings with Cassini VIMS

NASA Astrophysics Data System (ADS)

Clark, Roger Nelson; Cruikshank, D. P.; Jaumann, R.; Brown, R. H.; Dalle Ore, C.; Stephan, K.; Hoefen, T. M.; Curchin, J. M.; Buratti, B. J.; Filacchione, G.; Baines, K. H.; Nicholson, P. D.

2010-10-01

The Visual and Infrared Mapping Spectrometer (VIMS) on Cassini has obtained spatially resolved spectra on satellites of Saturn. The Cassini Rev 49 Iapetus fly-by on September 10, 2007, provided data on both the dark material and the transition zone between the dark material and the visually bright ice. The dark material has low albedo with a linear increase in reflectance with wavelength, 3-micron water, and CO2 absorptions. The transition between bright and dark regions shows mixing with unusual optical properties including increased blue scattering and increasing strength of a UV absorber in areas with stronger ice absorptions. Similar spectral effects are observed on other Saturnian satellites and in the rings. We have been unable to match these spectral properties and trends using tholins and carbon compounds. However, the dark material is spectrally matched by fine-grained metallic iron plus nano-phase hematite and adsorbed water which contribute UV and 3-micron absorption, respectively. The blue scattering peak and UV absorption can be explained by Rayleigh scattering from sub-micron particles with a UV absorption, or a combination of Rayleigh scattering and Rayleigh absorption as has been attributed to spectral properties of the Moon. A new radiative transfer model that includes Rayleigh scattering and Rayleigh absorption has been constructed. Models of ice, sub-micron metallic iron, hydrated iron oxide, and trace CO2 explain the observed spectra. Rayleigh absorption requires high absorption coefficient nano-sized particles, which is also consistent with metallic iron. The UV absorber appears to have increased strength on satellite surfaces close to Saturn, with a corresponding decrease in metallic iron signature. A possible explanation is that the iron is oxidized closer to Saturn by oxygen in the extended atmosphere of Saturn's rings, or the dark material is simply covered by clean fine-grained ice particles, for example, from the E-ring.

The Process of Nanostructuring of Metal (Iron) Matrix in Composite Materials for Directional Control of the Mechanical Properties

PubMed Central

Zemtsova, Elena

2014-01-01

We justified theoretical and experimental bases of synthesis of new class of highly nanostructured composite nanomaterials based on metal matrix with titanium carbide nanowires as dispersed phase. A new combined method for obtaining of metal iron-based composite materials comprising the powder metallurgy processes and the surface design of the dispersed phase is considered. The following stages of material synthesis are investigated: (1) preparation of porous metal matrix; (2) surface structuring of the porous metal matrix by TiC nanowires; (3) pressing and sintering to give solid metal composite nanostructured materials based on iron with TiC nanostructures with size 1–50 nm. This material can be represented as the material type “frame in the frame” that represents iron metal frame reinforcing the frame of different chemical compositions based on TiC. Study of material functional properties showed that the mechanical properties of composite materials based on iron with TiC dispersed phase despite the presence of residual porosity are comparable to the properties of the best grades of steel containing expensive dopants and obtained by molding. This will solve the problem of developing a new generation of nanostructured metal (iron-based) materials with improved mechanical properties for the different areas of technology. PMID:24695459

The process of nanostructuring of metal (iron) matrix in composite materials for directional control of the mechanical properties.

PubMed

Zemtsova, Elena; Yurchuk, Denis; Smirnov, Vladimir

2014-01-01

We justified theoretical and experimental bases of synthesis of new class of highly nanostructured composite nanomaterials based on metal matrix with titanium carbide nanowires as dispersed phase. A new combined method for obtaining of metal iron-based composite materials comprising the powder metallurgy processes and the surface design of the dispersed phase is considered. The following stages of material synthesis are investigated: (1) preparation of porous metal matrix; (2) surface structuring of the porous metal matrix by TiC nanowires; (3) pressing and sintering to give solid metal composite nanostructured materials based on iron with TiC nanostructures with size 1-50 nm. This material can be represented as the material type "frame in the frame" that represents iron metal frame reinforcing the frame of different chemical compositions based on TiC. Study of material functional properties showed that the mechanical properties of composite materials based on iron with TiC dispersed phase despite the presence of residual porosity are comparable to the properties of the best grades of steel containing expensive dopants and obtained by molding. This will solve the problem of developing a new generation of nanostructured metal (iron-based) materials with improved mechanical properties for the different areas of technology.

Nanoscale phase change memory materials.

PubMed

Caldwell, Marissa A; Jeyasingh, Rakesh Gnana David; Wong, H-S Philip; Milliron, Delia J

2012-08-07

Phase change memory materials store information through their reversible transitions between crystalline and amorphous states. For typical metal chalcogenide compounds, their phase transition properties directly impact critical memory characteristics and the manipulation of these is a major focus in the field. Here, we discuss recent work that explores the tuning of such properties by scaling the materials to nanoscale dimensions, including fabrication and synthetic strategies used to produce nanoscale phase change memory materials. The trends that emerge are relevant to understanding how such memory technologies will function as they scale to ever smaller dimensions and also suggest new approaches to designing materials for phase change applications. Finally, the challenges and opportunities raised by integrating nanoscale phase change materials into switching devices are discussed.

Effects of sulfate on heavy metal release from iron corrosion scales in drinking water distribution system.

PubMed

Sun, Huifang; Shi, Baoyou; Yang, Fan; Wang, Dongsheng

2017-05-01

Trace heavy metals accumulated in iron corrosion scales within a drinking water distribution system (DWDS) could potentially be released to bulk water and consequently deteriorate the tap water quality. The objective of this study was to identify and evaluate the release of trace heavy metals in DWDS under changing source water conditions. Experimental pipe loops with different iron corrosion scales were set up to simulate the actual DWDS. The effects of sulfate levels on heavy metal release were systemically investigated. Heavy metal releases of Mn, Ni, Cu, Pb, Cr and As could be rapidly triggered by sulfate addition but the releases slowly decreased over time. Heavy metal release was more severe in pipes transporting groundwater (GW) than in pipes transporting surface water (SW). There were strong positive correlations (R 2  > 0.8) between the releases of Fe and Mn, Fe and Ni, Fe and Cu, and Fe and Pb. When switching to higher sulfate water, iron corrosion scales in all pipe loops tended to be more stable (especially in pipes transporting GW), with a larger proportion of stable constituents (mainly Fe 3 O 4 ) and fewer unstable compounds (β-FeOOH, γ-FeOOH, FeCO 3 and amorphous iron oxides). The main functional iron reducing bacteria (IRB) communities were favorable for the formation of Fe 3 O 4 . The transformation of corrosion scales and the growth of sulfate reducing bacteria (SRB) accounted for the gradually reduced heavy metal release with time. The higher metal release in pipes transporting GW could be due to increased Fe 6 (OH) 12 CO 3 content under higher sulfate concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoscale surface modifications of medically relevant metals: state-of-the art and perspectives.

PubMed

Variola, Fabio; Brunski, John B; Orsini, Giovanna; Tambasco de Oliveira, Paulo; Wazen, Rima; Nanci, Antonio

2011-02-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently adopted to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. This review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately, the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, indeed, of all biomaterials.

Iron and alloys of iron. [lunar resources

NASA Technical Reports Server (NTRS)

Sastri, Sankar

1992-01-01

All lunar soil contains iron in the metallic form, mostly as an iron-nickel alloy in concentrations of a few tenths of 1 percent. Some of this free iron can be easily separated by magnetic means. It is estimated that the magnetic separation of 100,000 tons of lunar soil would yield 150-200 tons of iron. Agglutinates contain metallic iron which could be extracted by melting and made into powder metallurgy products. The characteristics and potential uses of the pure-iron and iron-alloy lunar products are discussed. Processes for working iron that might be used in a nonterrestrial facility are also addressed.

Evaluation of activated carbon fiber supported nanoscale zero-valent iron for chromium (VI) removal from groundwater in a permeable reactive column.

PubMed

Qu, Guangzhou; Kou, Liqing; Wang, Tiecheng; Liang, Dongli; Hu, Shibin

2017-10-01

An activated carbon fiber supported nanoscale zero-valent iron (ACF-nZVI) composite for Cr(VI) removal from groundwater was synthesized according to the liquid phase reduction method. The techniques of N 2 adsorption/desorption, FESEM, EDX, XRD and XPS were used to characterize the ACF-nZVI composite and the interaction between the ACF-nZVI composite and Cr(VI) ions. Batch experiments were conducted to evaluate the effects of several factors, including the amount of nZVI on activated carbon fiber (ACF), pH value, initial Cr(VI) concentration, and co-existing ions on Cr(VI) removal. The results indicate that presence of ACF can inhibit the aggregation of nanoscale zero-valent iron (nZVI) particles and increase its reactivity, and the Cr(VI) removal efficiency increases with increasing amounts of nZVI on ACF and a decrease in the initial Cr(VI) concentration. In acidic conditions, almost 100% of Cr(VI) in solution can be removed after 60 min of reaction, and the removal efficiency decreases with increasing initial pH values. The Cr(VI) removal is also dependent on the co-existing ions. Reusability experiments on ACF-nZVI demonstrate that the ACF-nZVI composite can keep a high reactivity after five successive reduction cycles. The removal mechanisms are proposed as a two-step interaction including the physical adsorption of Cr(VI) on the surface or inner layers of the ACF-nZVI composite and the subsequent reduction of Cr(VI) to Cr(III) by nZVI. Copyright © 2017 Elsevier Ltd. All rights reserved.

Contributions of Abiotic and Biotic Dechlorination Following Carboxymethyl Cellulose Stabilized Nanoscale Zero Valent Iron Injection.

PubMed

Kocur, Chris M D; Lomheim, Line; Boparai, Hardiljeet K; Chowdhury, Ahmed I A; Weber, Kela P; Austrins, Leanne M; Edwards, Elizabeth A; Sleep, Brent E; O'Carroll, Denis M

2015-07-21

A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection.

Immobilization of hexavalent chromium in contaminated soils using biochar supported nanoscale iron sulfide composite.

PubMed

Lyu, Honghong; Zhao, Hang; Tang, Jingchun; Gong, Yanyan; Huang, Yao; Wu, Qihang; Gao, Bin

2018-03-01

Biochar supported carboxymethyl cellulose (CMC)-stabilized nanoscale iron sulfide (FeS) composite (CMC-FeS@biochar) was prepared and tested for immobilization of hexavalent chromium Cr(VI) in soil. Results of UV-vis and transmission electron microscopy (TEM) showed that the backbone of biochar suppressed the aggregation of FeS, resulting in smaller particle size and more sorption sites than bare FeS. The composite at a dosage of 2.5 mg per gram soil displayed an enhanced Cr(VI) immobilization efficiency (a 94.7% reduction in the toxicity characteristic leaching procedure (TCLP) based leachability and a 95.6% reduction in the CaCl 2 extraction) compared to plain biochar and bare FeS. Sequential extraction procedure (SEP) and X-ray photoelectron spectroscopy (XPS) analysis suggested that CMC-FeS@biochar promoted the conversion of more accessible Cr (exchangeable and carbonate-bound fractions) into the less accessible forms (iron-manganese oxides-bound, organic material-bound, and residual fractions) to reduce the toxicity of Cr(VI) and that surface sorption and reduction were dominant mechanisms for Cr(VI) immobilization. CMC-FeS@biochar greatly reduced the bioavailability of Cr(VI) to wheat and earthworms (Eisenia fetida). Moreover, the application of CMC-FeS@biochar enhanced soil organic matter content and microbial activity. This work highlighted the potential of CMC-FeS@biochar composite as a low-cost, "green", and effective amendment for immobilizing Cr(VI) in contaminated soils and improving soil properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

Iron plaque formation and heavy metal uptake in Spartina alterniflora at different tidal levels and waterlogging conditions.

PubMed

Xu, Yan; Sun, Xiangli; Zhang, Qiqiong; Li, Xiuzhen; Yan, Zhongzheng

2018-05-30

Tidal flat elevation in the estuarine wetland determines the tidal flooding time and flooding frequency, which will inevitably affect the formation of iron plaque and accumulations of heavy metals (HMs) in wetland plants. The present study investigated the formation of iron plaque and HM's (copper, zinc, lead, and chromium) accumulation in S. alterniflora, a typical estuarine wetland species, at different tidal flat elevations (low, middle and high) in filed and at different time (3, 6, 9, 12 h per day) of waterlogging treatment in greenhouse conditions. Results showed that the accumulation of copper, zinc, lead, and chromium in S. alterniflora was proportional to the exchangeable fraction of these metals in the sediments, which generally increased with the increase of waterlogging time, whereas the formations of iron plaque in roots decreased with the increase of waterlogging time. Under field conditions, the uptake of copper and zinc in the different parts of the plants generally increased with the tidal levels despite the decrease in the metals' exchangeable fraction with increasing tidal levels. The formation of iron plaque was found to be highest in the middle tidal positions and significantly lower in low and high tidal positions. Longer waterlogging time increased the metals' accumulation but decreased the formation of iron plaque in S. alterniflora. The binding of metal ions on iron plaque helped impede the uptake and accumulation of copper and chromium in S. alterniflora. Copyright © 2018 Elsevier Inc. All rights reserved.

Rescuing iron-overloaded macrophages by conservative relocation of the accumulated metal

PubMed Central

Sohn, Yang-Sung; Mitterstiller, Anna-Maria; Breuer, William; Weiss, Guenter; Cabantchik, Z Ioav

2011-01-01

BACKGROUND AND PURPOSE Systemic iron deficiency concomitant with macrophage iron retention is characteristic of iron-refractory anaemias associated with chronic disease. The systemic misdistribution of iron, which is further exacerbated by parenteral iron supplementation, is mainly attributable to iron retention exerted on resident macrophages by hepcidin-mediated down-regulation of the iron exporter ferroportin. We aimed at developing an experimental macrophage-based cell model that recapitulates pathophysiological features of iron misdistribution found in chronic disorders and use it as a screening platform for identifying agents with the potential for relocating the accumulated metal and restoring affected functions. EXPERIMENTAL APPROACH A RAW macrophage subline was selected as cell model of iron retention based on their capacity to take up polymeric iron or aged erythrocytes excessively, resulting in a demonstrable increase of cell labile iron pools and oxidative damage that are aggravated by hepcidin. KEY RESULTS This model provided a three-stage high throughput screening platform for identifying agents with the combined ability to: (i) scavenge cell iron and thereby rescue macrophage cells damaged by iron-overload; (ii) bypass the ferroportin blockade by conveying the scavenged iron to other iron-starved cells in co-culture via transferrin but (iii) without promoting utilization of the scavenged iron by intracellular pathogens. As test agents we used chelators in clinical practice and found the oral chelator deferiprone fulfilled essentially all of the three criteria. CONCLUSIONS AND IMPLICATIONS We provide a proof of principle for conservative iron relocation as complementary therapeutic approach for correcting the misdistribution of iron associated with chronic disease and exacerbated by parenteral iron supplementation. PMID:21091647

Wheat straw biochar-supported nanoscale zerovalent iron for removal of trichloroethylene from groundwater.

PubMed

Li, Hui; Chen, Ya Qin; Chen, Shuai; Wang, Xiao Li; Guo, Shu; Qiu, Yue Feng; Liu, Yong Di; Duan, Xiao Li; Yu, Yun Jiang

2017-01-01

This study synthesized the wheat straw biochar-supported nanoscale zerovalent iron (BC-nZVI) via in-situ reduction with NaBH4 and biochar pyrolyzed at 600°C. Wheat straw biochar, as a carrier, significantly enhanced the removal of trichloroethylene (TCE) by nZVI. The pseudo-first-order rate constant of TCE removal by BC-nZVI (1.079 h-1) within 260 min was 1.4 times higher and 539.5 times higher than that of biochar and nZVI, respectively. TCE was 79% dechlorinated by BC-nZVI within 15 h, but only 11% dechlorinated by unsupported nZVI, and no TCE dechlorination occurred with unmodified biochar. Weakly acidic solution (pH 5.7-6.8) significantly enhanced the dechlorination of TCE. Chloride enhanced the removal of TCE, while SO42-, HCO3- and NO3- all inhibited it. Humic acid (HA) inhibited BC-nZVI reactivity, but the inhibition decreased slightly as the concentration of HA increased from 40 mg∙L-1 to 80 mg∙L-1, which was due to the electron shutting by HA aggregates. Results suggest that BC-nZVI was promising for remediation of TCE contaminated groundwater.

Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

PubMed

Zell, Thomas; Milstein, David

2015-07-21

The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in

Electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal

NASA Astrophysics Data System (ADS)

Kushkhov, Kh. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

2010-08-01

Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

Iron-based amorphous alloys and methods of synthesizing iron-based amorphous alloys

DOEpatents

Saw, Cheng Kiong; Bauer, William A.; Choi, Jor-Shan; Day, Dan; Farmer, Joseph C.

2016-05-03

A method according to one embodiment includes combining an amorphous iron-based alloy and at least one metal selected from a group consisting of molybdenum, chromium, tungsten, boron, gadolinium, nickel phosphorous, yttrium, and alloys thereof to form a mixture, wherein the at least one metal is present in the mixture from about 5 atomic percent (at %) to about 55 at %; and ball milling the mixture at least until an amorphous alloy of the iron-based alloy and the at least one metal is formed. Several amorphous iron-based metal alloys are also presented, including corrosion-resistant amorphous iron-based metal alloys and radiation-shielding amorphous iron-based metal alloys.

Performance of nanoscale zero-valent iron in nitrate reduction from water using a laboratory-scale continuous-flow system.

PubMed

Khalil, Ahmed M E; Eljamal, Osama; Saha, Bidyut Baran; Matsunaga, Nobuhiro

2018-04-01

Nanoscale zero-valent iron (nZVI) is a versatile treatment reagent that should be utilized in an effective application for nitrate remediation in water. For this purpose, a laboratory-scale continuous-flow system (LSCFS) was developed to evaluate nZVI performance in removal of nitrate in different contaminated-water bodies. The equipment design (reactor, settler, and polisher) and operational parameters of the LSCFS were determined based on nZVI characterization and nitrate reduction kinetics. Ten experimental runs were conducted at different dosages (6, 10 and 20 g) of nZVI-based reagents (nZVI, bimetallic nZVI-Cu, CuCl 2 -added nZVI). Effluent concentrations of nitrogen and iron compounds were measured, and pH and ORP values were monitored. The major role exhibited by the recirculation process of unreacted nZVI from the settler to the reactor succeeded in achieving overall nitrate removal efficiency (RE) of >90%. The similar performance of both nZVI and copper-ions-modified nZVI in contaminated distilled water was an indication of LSCFS reliability in completely utilizing iron nanoparticles. In case of treating contaminated river water and simulated groundwater, the nitrate reduction process was sensitive towards the presence of interfering substances that dropped the overall RE drastically. However, the addition of copper ions during the treatment counteracted the retardation effect and greatly enhanced the nitrate RE. Copyright © 2018 Elsevier Ltd. All rights reserved.

Removal of 2-ClBP from soil-water system using activated carbon supported nanoscale zerovalent iron.

PubMed

Zhang, Wei; Yu, Tian; Han, Xiaolin; Ying, Weichi

2016-09-01

We explored the feasibility and removal mechanism of removing 2-chlorobiphenyl (2-ClBP) from soil-water system using granular activated carbon (GAC) impregnated with nanoscale zerovalent iron (reactive activated carbon or RAC). The RAC samples were successfully synthesized by the liquid precipitation method. The mesoporous GAC based RAC with low iron content (1.32%) exhibited higher 2-ClBP removal efficiency (54.6%) in the water phase. The result of Langmuir-Hinshelwood kinetic model implied that the different molecular structures between 2-ClBP and trichloroethylene (TCE) resulted in more difference in dechlorination reaction rates on RAC than adsorption capacities. Compared to removing 2-ClBP in the water phase, RAC removed the 2-ClBP more slowly in the soil phase due to the significant external mass transfer resistance. However, in the soil phase, a better removal capacity of RAC was observed than its base GAC because the chemical dechlorination played a more important role in total removal process for 2-ClBP. This important result verified the effectiveness of RAC for removing 2-ClBP in the soil phase. Although reducing the total RAC removal rate of 2-ClBP, soil organic matter (SOM), especially the soft carbon, also served as an electron transfer medium to promote the dechlorination of 2-ClBP in the long term. Copyright © 2016. Published by Elsevier B.V.

Reduction of aqueous Crvi using nanoscale zero-valent iron dispersed by high energy electron beam irradiation

NASA Astrophysics Data System (ADS)

Zhang, Jing; Zhang, Guilong; Wang, Min; Zheng, Kang; Cai, Dongqing; Wu, Zhengyan

2013-09-01

High energy electron beam (HEEB) irradiation was used to disperse nanoscale zero-valent iron (NZVI) for reduction of Crvi to Criii in aqueous solution. Pore size distribution, scanning electron microscopy and X-ray diffraction characterizations demonstrated that HEEB irradiation could effectively increase the dispersion of NZVI resulting in more active reduction sites of Crvi on NZVI. Batch reduction experiments indicated that the reductive capacity of HEEB irradiation-modified NZVI (IMNZVI) was significantly improved, as the reductive efficiency reached 99.79% under the optimal conditions (electron beam dose of 30 kGy at 10 MeV, pH 2.0 and 313 K) compared with that of raw NZVI (72.14%). Additionally, the NZVI was stable for at least two months after irradiation. The modification mechanism of NZVI by HEEB irradiation was investigated and the results indicated that charge and thermal effects might play key roles in dispersing the NZVI particles.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

Transport of carboxymethyl cellulose stabilized nanoscale zerovalent iron in porous media, an experimental and modeling study

NASA Astrophysics Data System (ADS)

Sleep, Brent; Mondal, Pulin; Furbacher, Paul; Cui, Ziteng; Krol, Magdalena

2015-04-01

Nano-scale zero valent iron (nZVI) is capable of reacting with a wide variety of groundwater contaminants. Therefore, during the last decade nZVI has received significant attention for application in subsurface remediation, particularly for sites contaminated with chlorinated compounds and heavy metals. However, due to agglomeration of the nZVI, delivery into the contaminated subsurface zones is challenging. Polymer stabilization of nZVI can enhance the mobility of the iron particles in the subsurface. In this study, a set of laboratory-scale transport experiments and numerical simulations were performed to evaluate carboxymethyl cellulose (CMC) polymer stabilized nZVI transport in porous media. Experiments were conducted in a two-dimensional water-saturated lab-scale glass-walled sandbox, uniformly packed with silica sand, to identify the effects of water specific discharge and CMC concentration on nZVI transport. Experiments were also performed using Lissamine Green B (LGB) dye as a non-reactive tracer to characterize the sand media. The CMC stabilized nZVI was synthesized freshly at a concentration of 1000 mg/L before each transport experiment. The synthesized CMC-nZVI mixture was characterized using transmission electron microscopy, dynamic light scattering, and UV-visual spectrophotometry. The movement of the LGB dye and nZVI in the sandbox during the experiments was monitored using time-lapsed images captured using a light source and a dark box. The transport of LGB, CMC, and CMC-nZVI was evaluated through analysis of the breakthrough curves at the outlet and the retained nZVI in the sandbox. The LGB, CMC, and nZVI transport was also modeled using a multiphase flow and transport model considering LGB and CMC as solutes, and nZVI as a colloid. Analysis of the breakthrough data showed that the mass recovery of LGB and CMC was greater than 95 % indicating conservative transport in silica sand. However, the mean residence time of CMC was significantly higher than

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

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

Schneibel, Joachim H.

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1450.degree. C. for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

DOEpatents

Schneibel, J.H.

1997-06-10

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

Metal matrix composite of an iron aluminide and ceramic particles and method thereof

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

Schneibel, J.H.

A metal matrix composite comprising an iron aluminide binder phase and a ceramic particulate phase such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide is made by heating a mixture of iron aluminide powder and particulates of one of the ceramics such as titanium diboride, zirconium diboride, titanium carbide and tungsten carbide in a alumina crucible at about 1,450 C for about 15 minutes in an evacuated furnace and cooling the mixture to room temperature. The ceramic particulates comprise greater than 40 volume percent to about 99 volume percent of the metal matrix composite.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission

NASA Astrophysics Data System (ADS)

Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

2011-08-01

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications.Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO2 and In2O3 are used as examples. We also show that linear chains of short ZnO nanorods embedded in

DIVALENT METAL TRANSPORTER-1 REGULATION BY IRON AND VANADIUM MODULATES HYDROGEN PEROXIDE-INDUCED DNA DAMAGE IN LUNG CELLS

EPA Science Inventory

The divalent metal transporter-1 (DMT1) participates in the detoxification of metals that can damage lung epithelium. Elevated iron levels increase the expression of DMT1 in bronchial epithelial cells stimulating its uptake and storage in ferritin, thus making iron unavailable t...

Nanoscale On-Silico Electron Transport via Ferritins.

PubMed

Bera, Sudipta; Kolay, Jayeeta; Banerjee, Siddhartha; Mukhopadhyay, Rupa

2017-02-28

Silicon is a solid-state semiconducting material that has long been recognized as a technologically useful one, especially in electronics industry. However, its application in the next-generation metalloprotein-based electronics approaches has been limited. In this work, the applicability of silicon as a solid support for anchoring the iron-storage protein ferritin, which has a semiconducting iron nanocore, and probing electron transport via the ferritin molecules trapped between silicon substrate and a conductive scanning probe has been investigated. Ferritin protein is an attractive bioelectronic material because its size (X-ray crystallographic diameter ∼12 nm) should allow it to fit well in the larger tunnel gaps (>5 nm), fabrication of which is relatively more established, than the smaller ones. The electron transport events occurring through the ferritin molecules that are covalently anchored onto the MPTMS-modified silicon surface could be detected at the molecular level by current-sensing atomic force spectroscopy (CSAFS). Importantly, the distinct electronic signatures of the metal types (i.e., Fe, Mn, Ni, and Au) within the ferritin nanocore could be distinguished from each other using the transport band gap analyses. The CSAFS measurements on holoferritin, apoferritin, and the metal core reconstituted ferritins reveal that some of these ferritins behave like n-type semiconductors, while the others behave as p-type semiconductors. The band gaps for the different ferritins are found to be within 0.8 to 2.6 eV, a range that is valid for the standard semiconductor technology (e.g., diodes based on p-n junction). The present work indicates effective on-silico integration of the ferritin protein, as it remains functionally viable after silicon binding and its electron transport activities can be detected. Potential use of the ferritin-silicon nanohybrids may therefore be envisaged in applications other than bioelectronics, too, as ferritin is a versatile

High efficiency iron electrode and additives for use in rechargeable iron-based batteries

DOEpatents

Narayan, Sri R.; Prakash, G. K. Surya; Aniszfeld, Robert; Manohar, Aswin; Malkhandi, Souradip; Yang, Bo

2017-02-21

An iron electrode and a method of manufacturing an iron electrode for use in an iron-based rechargeable battery are disclosed. In one embodiment, the iron electrode includes carbonyl iron powder and one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery. An iron-air rechargeable battery including an iron electrode comprising carbonyl iron is also disclosed, as is an iron-air battery wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

Foam-assisted delivery of nanoscale zero valent iron in porous media

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

Ding, Yuanzhao; Liu, Bo; Shen, Xin

2013-09-01

Foam is potentially a promising vehicle to deliver nanoparticles for vadose zone remediation as foam can overcome the intrinsic problems associated with solution-based delivery, such as preferential flow and contaminant mobilization. In this work, the feasibility of using foam to deliver nanoscale zero valent iron (nZVI) in unsaturated porous media was investigated. Foams generated using surfactant sodium lauryl ether sulfate (SLES) showed excellent ability to carry nZVI. SLES and nZVI concentrations in the foaming solutions did not affect the percentages of nZVI concentrations in foams relative to nZVI concentrations in the solutions. When foams carrying nZVI were injected through themore » unsaturated columns, the fractions of nZVI exiting the column were much higher than those when nZVI was injected in liquid. The enhanced nZVI transport implies that foam delivery could significantly increase the radius of influence of injected nZVI. The type and concentrations of surfactants and the influent nZVI concentrations did not noticeably affect nZVI transport during foam delivery. In contrast, nZVI retention increased considerably as the grain size of porous media decreased. Oxidation of foam-delivered nZVI due to oxygen diffusion into unsaturated porous media was visually examined using a flow cell. It was demonstrated that if foams are injected to cover a deep vadose zone layer, oxidation would only cause a small fraction of foam-delivered nZVI to be oxidized before it reacts with contaminants.« less

Nanoscale surface modifications of medically-relevant metals: state-of-the art and perspectives

PubMed Central

Variola, Fabio; Brunski, John; Orsini, Giovanna; de Oliveira, Paulo Tambasco; Wazen, Rima; Nanci, Antonio

2011-01-01

Evidence that nanoscale surface properties stimulate and guide various molecular and biological processes at the implant/tissue interface is fostering a new trend in designing implantable metals. Cutting-edge expertise and techniques drawn from widely separated fields, such as nanotechnology, materials engineering and biology, have been advantageously exploited to nanoengineer surfaces in ways that control and direct these processes in predictable manners. In this review, we present and discuss the state-of-the-art of nanotechnology-based approaches currently used to modify the surface of metals used for orthopedic and dental applications, and also briefly consider their use in the cardiovascular field. The effects of nanoengineered surfaces on various in vitro molecular and cellular events are firstly discussed. Importantly, this review also provides an overview of in vivo and clinical studies with nanostructured metallic implants, and addresses the potential influence of nanotopography on biomechanical events at interfaces. Ultimately the objective of this work is to give the readership a comprehensive picture of the current advances, future developments and challenges in the application of the infinitesimally small to biomedical surface science. We believe that an integrated understanding of the in vitro and particularly of the in vivo behavior is mandatory for the proper exploitation of nanostructured implantable metals and, as a matter of fact, all biomaterials. PMID:20976359

Nanoscale strengthening mechanisms in metallic thin film systems

NASA Astrophysics Data System (ADS)

Schoeppner, Rachel Lynn

Nano-scale strengthening mechanisms for thin films were investigated for systems governed by two different strengthening techniques: nano-laminate strengthening and oxide dispersion strengthening. Films were tested under elevated temperature conditions to investigate changes in deformation mechanisms at different operating temperatures, and the structural stability. Both systems exhibit remarkable stability after annealing and thus long-term reliability. Nano-scale metallic multilayers with smaller layer thicknesses show a greater relative resistance to decreasing strength at higher temperature testing conditions than those with larger layer thicknesses. This is seen in both Cu/Ni/Nb multilayers as well as a similar tri-component bi-layer system (Cu-Ni/Nb), which removed the coherent interface from the film. Both nanoindentation and micro-pillar compression tests investigated the strain-hardening ability of these two systems to determine what role the coherent interface plays in this mechanism. Tri-layer films showed a higher strain-hardening ability as the layer thickness decreased and a higher strain-hardening exponent than the bi-layer system: verifying the presence of a coherent interface increases the strain-hardening ability of these multilayer systems. Both systems exhibited hardening of the room temperature strength after annealing, suggesting a change in microstructure has occurred, unlike that seen in other multilayer systems. Oxide dispersion strengthened Au films showed a marked increase in hardness and wear resistance with the addition of ZnO particles. The threshold for stress-induced grain-refinement as opposed to grain growth is seen at concentrations of at least 0.5 vol%. These systems exhibited stable microstructures during thermal cycling in films containing at least 1.0%ZnO. Nanoindentation experiments show the drop in hardness following annealing is almost completely attributed to the resulting grain growth. Four-point probe resistivity

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

The Effect of Time on the Stability of Iron Oxide Nanoparticles in Environmental Acids.

PubMed

Rabajczyk, Anna; El Yamani, Naouale; Dusinska, Maria

2017-05-01

  Advanced technologies seek for development of new materials and substances with extraordinary physicochemical properties at nanoscale level that boosts their increased use in everyday life. Manufacture of metal nanomaterials, including iron, carries the risk of their emission to surface waters. Suspended particulate matter (SPM) plays an important role in the transport of pollutants, such as metals which are an essential component of surface waters. The humic substances (HA), part of the SPM, interact with metal ions present in the aquatic environment. However, the previously available data on these compounds were obtained at the macro level and only scant information exist on nanomaterials. Thus, the present work has focused on the relationship between humic substances and nanosized particles, such as n-Fe2O3, in environmental acids.

Nanoscale semiconductor-insulator-metal core/shell heterostructures: facile synthesis and light emission.

PubMed

Li, Gong Ping; Chen, Rui; Guo, Dong Lai; Wong, Lai Mun; Wang, Shi Jie; Sun, Han Dong; Wu, Tom

2011-08-01

Controllably constructing hierarchical nanostructures with distinct components and designed architectures is an important theme of research in nanoscience, entailing novel but reliable approaches of bottom-up synthesis. Here, we report a facile method to reproducibly create semiconductor-insulator-metal core/shell nanostructures, which involves first coating uniform MgO shells onto metal oxide nanostructures in solution and then decorating them with Au nanoparticles. The semiconductor nanowire core can be almost any material and, herein, ZnO, SnO(2) and In(2)O(3) are used as examples. We also show that linear chains of short ZnO nanorods embedded in MgO nanotubes and porous MgO nanotubes can be obtained by taking advantage of the reduced thermal stability of the ZnO core. Furthermore, after MgO shell-coating and the appropriate annealing treatment, the intensity of the ZnO near-band-edge UV emission becomes much stronger, showing a 25-fold enhancement. The intensity ratio of the UV/visible emission can be increased further by decorating the surface of the ZnO/MgO nanowires with high-density plasmonic Au nanoparticles. These heterostructured semiconductor-insulator-metal nanowires with tailored morphologies and enhanced functionalities have great potential for use as nanoscale building blocks in photonic and electronic applications. This journal is © The Royal Society of Chemistry 2011

Transport of Lactate-modified Nanoscale Iron Particles in Porous Media

NASA Astrophysics Data System (ADS)

Reddy, K. R.

2012-12-01

Nanoscale iron particles (NIP) have recently shown to be effective for dehalogenation of recalcitrant organic contaminants such as pentachlorphenol (PCP) and dinitrotoluene (DNT) in the environment. However, effective transport of NIP into the contaminated subsurface zones is crucial for the success of in-situ remediation. Previous studies showed that the transport of NIP in soils is very limited and surface-modification of NIP is required to achieve adequate transport. This paper investigates the transport of NIP and lactate-modified NIP (LMNIP) through four different porous media (sands with different particle size and distribution). A series of laboratory column experiments was conducted to quantify the transport of NIP and LMNIP at two different slurry concentrations of 1 g/L and 4 g/L under two different flow velcoities. NIP used in this study possessed magentic properties, thus a magnetic susceptibility sensor system was used to monitor the changes in magnetic susceptibility (MS) along the length of the column at different times during the experiments. At the end of testing, the distribution of total Fe in the sand column was measured. Results showed a linear correlation between the Fe concentration and MS and it was used to assess the transient transport of NIP and LMNIP in the sand columns. Results showed that LMNIP transported better than bare NIP and higher concentration of 4 g/L LMNIP exhibited unform and greater transport compared to other tested conditions. Transport of NIP increased in the order from fine Ottawa sand > medium field sand > coarse field sand > coarse Ottawa sand. Filtration theory and advective-dispersion equation with reaction were applied to capture the transport response of NIP and LMNIP in the sand columns.

System and method for making metallic iron with reduced CO.sub.2 emissions

DOEpatents

Kiesel, Richard F; Englund, David J; Schlichting, Mark; Meehan, John; Crouch, Jeremiah; Wilson, Logan

2014-10-14

A method and system for making metallic iron nodules with reduced CO.sub.2 emissions is disclosed. The method includes: assembling a linear hearth furnace having entry and exit portions, at least a conversion zone and a fusion zone, and a moving hearth adapted to move reducible iron bearing material through the furnace on contiguous hearth sections; assembling a shrouded return substantially free of air ingress extending adjacent at least the conversion and fusion zones of the furnace through which hearth sections can move from adjacent the exit portion to adjacent the entry portion of the furnace; transferring the hearth sections from the furnace to the shrouded return adjacent the exit portion; reducing reducible material in the linear hearth furnace to metallic iron nodules; and transporting gases from at least the fusion zone to the shrouded return to heat the hearth sections while in the shrouded return.

Ecotoxicity and environmental safety related to nano-scale zerovalent iron remediation applications.

PubMed

Semerád, Jaroslav; Cajthaml, Tomáš

2016-12-01

This mini-review summarizes the current information that has been published on the various effects of nano-scale zerovalent iron (nZVI) on microbial biota, with an emphasis on reports that highlight the positive aspects of its application or its stimulatory effects on microbiota. By nature, nZVI is a highly reactive substance; thus, the possibility of nZVI being toxic is commonly suspected. Accordingly, the cytotoxicity of nZVI and the toxicity of nZVI-related products have been detected by laboratory tests and documented in the literature. However, there are numerous other published studies on its useful nature, which are usually skipped in reviews that deal only with the phenomenon of toxicity. Therefore, the objective of this article is to review both recent publications reporting the toxic effects of nZVI on microbiota and studies documenting the positive effects of nZVI on various environmental remediation processes. Although cytotoxicity is an issue of general importance and relevance, nZVI can reduce the overall toxicity of a contaminated site, which ultimately results in the creation of better living conditions for the autochthonous microflora. Moreover, nZVI changes the properties of the site in a manner such that it can also be used as a tool in a tailor-made approach to support a specific microbial community for the decontamination of a particular polluted site.

Impact of the morphology and reactivity of nanoscale zero-valent iron (NZVI) on dechlorinating bacteria.

PubMed

Rónavári, Andrea; Balázs, Margit; Tolmacsov, Péter; Molnár, Csaba; Kiss, István; Kukovecz, Ákos; Kónya, Zoltán

2016-05-15

Nanoscale zero-valent iron (NZVI) is increasingly used for reducing chlorinated organic contaminants in soil or groundwater. However, little is known about what impact the particles will have on the biochemical processes and the indigenous microbial communities. Nanoiron reactivity is affected by the structure and morphology of nanoparticles that complicates the applicability in bioremediation. In this study, the effect of precursors (ferrous sulfate and ferric chloride) and reducing agents (sodium dithionite and sodium borohydride) on the morphology and the reactivity of NZVIs was investigated. We also studied the impact of differently synthesized NZVIs on microbial community, which take part in reductive dechlorination. We demonstrated that both the applied iron precursor and the reducing agent had influence on the structure of the nanoparticles. Spherical nanoparticles with higher Fe(0) content (>90%) was observed by using sodium borohydride as reducing agent, while application of sodium dithionite as reducing agent resulted nanostructures with lower Fe(0) content (between 68,7 and 85,5%). To determine the influence of differently synthesized NZVIs on cell viability anaerobic enriched microcosm were used. NVZI was used in 0.1 g/L concentration in all batch experiments. Relative amount of Dehalococcoides, sulfate reducers (SRBs) and methanogens were measured by quantitative PCR. We found that the relative amount of Dehalococcoides slowly decreased in all experiments independently from the precursor and reducing agent, whereas the total amount of microbes increased. The only clear distinction was in relative amount of sulfate reducers which were higher in the presence of NZVIs synthesized from sodium dithionite. Copyright © 2016 Elsevier Ltd. 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

A Thermal Diode Based on Nanoscale Thermal Radiation.

PubMed

Fiorino, Anthony; Thompson, Dakotah; Zhu, Linxiao; Mittapally, Rohith; Biehs, Svend-Age; Bezencenet, Odile; El-Bondry, Nadia; Bansropun, Shailendra; Ben-Abdallah, Philippe; Meyhofer, Edgar; Reddy, Pramod

2018-05-23

In this work we demonstrate thermal rectification at the nanoscale between doped Si and VO 2 surfaces. Specifically, we show that the metal-insulator transition of VO 2 makes it possible to achieve large differences in the heat flow between Si and VO 2 when the direction of the temperature gradient is reversed. We further show that this rectification increases at nanoscale separations, with a maximum rectification coefficient exceeding 50% at ∼140 nm gaps and a temperature difference of 70 K. Our modeling indicates that this high rectification coefficient arises due to broadband enhancement of heat transfer between metallic VO 2 and doped Si surfaces, as compared to narrower-band exchange that occurs when VO 2 is in its insulating state. This work demonstrates the feasibility of accomplishing near-field-based rectification of heat, which is a key component for creating nanoscale radiation-based information processing devices and thermal management approaches.

Wheat straw biochar-supported nanoscale zerovalent iron for removal of trichloroethylene from groundwater

PubMed Central

Li, Hui; Chen, Ya Qin; Chen, Shuai; Wang, Xiao Li; Guo, Shu; Qiu, Yue Feng; Liu, Yong Di; Duan, Xiao Li; Yu, Yun Jiang

2017-01-01

This study synthesized the wheat straw biochar-supported nanoscale zerovalent iron (BC-nZVI) via in-situ reduction with NaBH4 and biochar pyrolyzed at 600°C. Wheat straw biochar, as a carrier, significantly enhanced the removal of trichloroethylene (TCE) by nZVI. The pseudo-first-order rate constant of TCE removal by BC-nZVI (1.079 h−1) within 260 min was 1.4 times higher and 539.5 times higher than that of biochar and nZVI, respectively. TCE was 79% dechlorinated by BC-nZVI within 15 h, but only 11% dechlorinated by unsupported nZVI, and no TCE dechlorination occurred with unmodified biochar. Weakly acidic solution (pH 5.7–6.8) significantly enhanced the dechlorination of TCE. Chloride enhanced the removal of TCE, while SO42−, HCO3− and NO3− all inhibited it. Humic acid (HA) inhibited BC-nZVI reactivity, but the inhibition decreased slightly as the concentration of HA increased from 40 mg∙L-1 to 80 mg∙L-1, which was due to the electron shutting by HA aggregates. Results suggest that BC-nZVI was promising for remediation of TCE contaminated groundwater. PMID:28264061

Interlocked by nanoscale sculpturing: pure aluminum copper contacts (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gerngross-Baytekin, Melike; Gerngross, Mark Daniel; Carstensen, Jürgen; Adelung, Rainer

2017-06-01

Connecting metals reliable with different corrosion potential is a well-known challenge. An extreme example are copper aluminum contacts. Galvanic corrosion occurs if the two different metals are in contact with each other and an electrolyte, the aluminum becomes susceptible to corrosion under current flow. Usually, antioxidant pastes containing metals are employed but create difficulties e.g. for fatigue resistant power electronic connections. The recently described process of nanoscale sculpturing [1] offers an alternative. Usually, if the surface of metals like aluminium are prepared they are just arbitrary cuts through the bulk. There is no optimization of the surface grain structure towards stability at all. Neither the crystalline facets in the grains are in their most stable orientation nor is the protective oxide shell the most stable one. The nanoscale sculpturing approach is carving out the most stable grains and planes by chemical or electrochemical treatment. The decisive trick is that the chemistry is targeting towards the instable oxide and not the metal. Aluminium sample surfaces including alloys like AA575 exhibit afterwards single crystalline surface facets covered with nanoscale stable oxide films. Galvanically deposited copper forms extremely reliable interlocked connections on top, even allowing for soldering on top of their surface.

Removal of nitrobenzene by immobilized nanoscale zero-valent iron: Effect of clay support and efficiency optimization

NASA Astrophysics Data System (ADS)

Li, Xiaoguang; Zhao, Ying; Xi, Beidou; Mao, Xuhui; Gong, Bin; Li, Rui; Peng, Xing; Liu, Hongliang

2016-05-01

In this study, natural clays were used as the support for nanoscale zero-valent iron (nZVI) to fulfill affordable and efficient decontamination materials. In comparison with the kaolinite (K) and montmorillonite (M) supported nZVI materials (K-nZVI and M-nZVI), Hangjin clay supported nZVI (HJ-nZVI) exhibited the best performance for nitrobenzene (NB) removal because of its favorable characteristics, such as higher specific surface area (SSA, 82.0 m2 g-1), larger pore volume (0.1198 cm3 g-1) and bigger average pore diameter (6.2 nm). The NB removal efficiency achieved by HJ-nZVI (93.2 ± 2.8%) was much higher than these achieved by HJ clay alone (38.2 ± 2.3%), nZVI alone (52.3 ± 2.5%) and by the combined use of nZVI and HJ clay (70.2 ± 1.3%). The superior performance of HJ-nZVI was associated with three aspects: the even distribution of nZVIs onto HJ clay, higher payload efficiency of nZVIs and the stronger adsorption capability of HJ clay support. Higher SSA, larger pore volume, favorable cation exchange capacity and structural negative charges all facilitated the payload of iron onto HJ clay. The adsorption process accelerated the reduction via increasing the local concentration of aqueous NB. The high efficiency of HJ-nZVI for decontamination warranted its promising prospect in remediation applications.

Effects of nitrate on the treatment of lead contaminated groundwater by nanoscale zerovalent iron.

PubMed

Su, Yiming; Adeleye, Adeyemi S; Zhou, Xuefei; Dai, Chaomeng; Zhang, Weixian; Keller, Arturo A; Zhang, Yalei

2014-09-15

Nanoscale zerovalent iron (nZVI) is efficient for removing Pb(2+) and nitrate from water. However, the influence of nitrate, a common groundwater anion, on Pb(2+) removal by nZVI is not well understood. In this study, we showed that under excess Fe(0) conditions (molar ratio of Fe(0)/nitrate>4), Pb(2+) ions were immobilized more quickly (<5 min) than in nitrate-free systems (∼ 15 min) due to increasing pH. With nitrate in excess (molar ratio of Fe(0)/nitrate<4), nitrate stimulated the formation of crystal PbxFe3-xO4 (ferrite), which provided additional Pb(2+) removal. However, ∼ 7% of immobilized Pb(2+) ions were released into aqueous phase within 2h due to ferrite deformation. Oxidation-reduction potential (ORP) values below -600 mV correlated with excess Fe(0) conditions (complete Pb(2+) immobilization), while ORP values ≥-475 mV characterized excess nitrate conditions (ferrite process and Pb(2+) release occurrence). This study indicates that ORP monitoring is important for proper management of nZVI-based remediation in the subsurface to avoid lead remobilization in the presence of nitrate. Copyright © 2014 Elsevier B.V. All rights reserved.

Towards nanoprinting with metals on graphene.

PubMed

Melinte, G; Moldovan, S; Hirlimann, C; Liu, X; Bégin-Colin, S; Bégin, D; Banhart, F; Pham-Huu, C; Ersen, O

2015-08-28

Graphene and carbon nanotubes are envisaged as suitable materials for the fabrication of the new generation of nanoelectronics. The controlled patterning of such nanostructures with metal nanoparticles is conditioned by the transfer between a recipient and the surface to pattern. Electromigration under the impact of an applied voltage stands at the base of printing discrete digits at the nanoscale. Here we report the use of carbon nanotubes as nanoreservoirs for iron nanoparticles transfer on few-layer graphene. An initial Joule-induced annealing is required to ensure the control of the mass transfer with the nanotube acting as a 'pen' for the writing process. By applying a voltage, the tube filled with metal nanoparticles can deposit metal on the surface of the graphene sheet at precise locations. The reverse transfer of nanoparticles from the graphene surface to the nanotube when changing the voltage polarity opens the way for error corrections.

Towards nanoprinting with metals on graphene

NASA Astrophysics Data System (ADS)

Melinte, G.; Moldovan, S.; Hirlimann, C.; Liu, X.; Bégin-Colin, S.; Bégin, D.; Banhart, F.; Pham-Huu, C.; Ersen, O.

2015-08-01

Graphene and carbon nanotubes are envisaged as suitable materials for the fabrication of the new generation of nanoelectronics. The controlled patterning of such nanostructures with metal nanoparticles is conditioned by the transfer between a recipient and the surface to pattern. Electromigration under the impact of an applied voltage stands at the base of printing discrete digits at the nanoscale. Here we report the use of carbon nanotubes as nanoreservoirs for iron nanoparticles transfer on few-layer graphene. An initial Joule-induced annealing is required to ensure the control of the mass transfer with the nanotube acting as a `pen' for the writing process. By applying a voltage, the tube filled with metal nanoparticles can deposit metal on the surface of the graphene sheet at precise locations. The reverse transfer of nanoparticles from the graphene surface to the nanotube when changing the voltage polarity opens the way for error corrections.

The magnetohydrodynamic force experienced by spherical iron particles in liquid metal

NASA Astrophysics Data System (ADS)

Ščepanskis, Mihails; Jakovičs, Andris

2016-04-01

The paper contains a theoretical investigation of magnetohydrodynamic force experienced by iron particles (well-conducting and ferromagnetic) in well-conducting liquid. The investigation is performed by extending the Leenov and Kolin's theory to take into account the second-order effect. Therefore, the limits of the parent model are taken over to the present results. It is found that the effective conductivity of iron particles in liquid metal, which is important for practical application of the theoretically obtained force, is approximately equal to 1.5·106 S/m. The last result is obtained using a quasi-empirical approach - a comparison of experimental results with the results of the numerical simulation that was performed for various conductivities of the iron particles.

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.

A Comparative Study of the Adsorption of Methylene Blue onto Synthesized Nanoscale Zero-Valent Iron-Bamboo and Manganese-Bamboo Composites

PubMed Central

Shaibu, Solomon E.; Adekola, Folahan A.; Adegoke, Halimat I.; Ayanda, Olushola S.

2014-01-01

In this study, bamboo impregnated with nanoscale zero-valent iron (nZVI) and nanoscale manganese (nMn) were prepared by the aqueous phase borohydride reduction method and characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and PIXE analysis. The synthesized nMn-bamboo and nZVI-bamboo composites were subsequently applied to the sorption of methylene blue (MB) dye from aqueous solution. The adsorption of MB dye was investigated under various experimental conditions such as pH, contact time, initial concentration of MB dye and adsorbent dosage. The results showed that the synthesized nZVI-bamboo composite was more effective than nMn-bamboo composite in terms of higher MB dye adsorption capacity of 322.5 mg/g compared to 263.5 mg/g of nMn-bamboo composite. At a concentration of 140 mg/L MB dye, 0.02 g of nZVI-bamboo and nMn-bamboo composites resulted in 79.6% and 78.3% removal, respectively, at 165 rpm, contact time of 120 min and at a solution pH of 7.6. The equilibrium data was best represented by Freundlich isotherm model and the pseudo-second order kinetic model better explained the kinetic data for both nZVI-bamboo and nMn-bamboo composites. PMID:28788688

Controlled assembly of graphene-capped nickel, cobalt and iron silicides

PubMed Central

Vilkov, O.; Fedorov, A.; Usachov, D.; Yashina, L. V.; Generalov, A. V.; Borygina, K.; Verbitskiy, N. I.; Grüneis, A.; Vyalikh, D. V.

2013-01-01

The unique properties of graphene have raised high expectations regarding its application in carbon-based nanoscale devices that could complement or replace traditional silicon technology. This gave rise to the vast amount of researches on how to fabricate high-quality graphene and graphene nanocomposites that is currently going on. Here we show that graphene can be successfully integrated with the established metal-silicide technology. Starting from thin monocrystalline films of nickel, cobalt and iron, we were able to form metal silicides of high quality with a variety of stoichiometries under a Chemical Vapor Deposition grown graphene layer. These graphene-capped silicides are reliably protected against oxidation and can cover a wide range of electronic materials/device applications. Most importantly, the coupling between the graphene layer and the silicides is rather weak and the properties of quasi-freestanding graphene are widely preserved. PMID:23835625

Nanoscale zero-valent iron incorporated with nanomagnetic diatomite for catalytic degradation of methylene blue in heterogeneous Fenton system.

PubMed

Zha, Yiming; Zhou, Ziqing; He, Haibo; Wang, Tianlin; Luo, Liqiang

2016-01-01

Nanoscale zero-valent iron (nZVI) incorporated with nanomagnetic diatomite (DE) composite material was prepared for catalytic degradation of methylene blue (MB) in heterogeneous Fenton system. The material was constructed by two facile steps: Fe3O4 magnetic nanoparticles were supported on DE by chemical co-precipitation method, after which nZVI was incorporated into magnetic DE by liquid-phase chemical reduction strategy. The as-prepared catalyst was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, magnetic properties measurement and nitrogen adsorption-desorption isotherm measurement. The novel nZVI@Fe3O4-diatomite nanocomposites showed a distinct catalytic activity and a desirable effect for degradation of MB. MB could be completely decolorized within 8 min and the removal efficiency of total organic carbon could reach to 90% after reaction for 1 h.

Understanding of the Formation of Micro/Nanoscale Structures on Metal Surfaces by Ultrafast Pulse Laser Processing

NASA Astrophysics Data System (ADS)

Peng, Edwin

In the recent decades, there has been much interest in functionalized surfaces produced by ultrafast laser processing. Using pulse lasers with nanosecond to femtosecond time scale, a wide range of micro/nanoscale structures can be produced on virtually all metal surfaces. These surface structures create special optoelectronic, wetting, and tribological properties with a diverse range of potential applications. The formation mechanisms of these surface structures, especially microscale, mound-like structures, are not fully understood. There has been wide study of ultrafast laser processing of metals. Yet, the proposed formation models present in current literature often lack sufficient experimental verification. Specifically, many studies are limited to surface characterization, e.g. scanning electron microscopy of the surfaces of these micro/nanoscale structures. Valuable insight into the physical processes responsible for formation can be obtained if standard material science characterization methods are performed across the entire mound. In our study, we examined mound-like structures formed on three metal alloys. Using cross section and 3D slice and view operations by a dual beam scanning electron microscope-focused ion beam, the interior microstructures of these mounds are revealed. Taking advantage of amorphous phase formation during laser processing of Ni60Nb40, we verified the fluence-dependent formation model: mounds formed at low fluence are primarily the result of ablation while mounds formed at high fluence are formed by both ablation and rapid resolidification by hydrodynamical fluid flow. For the first time, we revealed the cross section of a wide variety of mound-like structures on titanium surfaces. The increased contribution to mound formation by fluid flow with increasing fluence was observed. Finally, a 3D scanning electron microscopy technique was applied for mounds produced on silver surface by delayed-pulse laser processing. The interior

Interaction between tungsten monocarbide and an iron-based metallic melt

NASA Astrophysics Data System (ADS)

Chumanov, I. V.; Anikeev, A. N.

2015-12-01

A technique and results of investigation of compacted tungsten carbide substrates by scanning microscopy are reported. Samples are prepared in the course of studies of the wettability of tungsten carbide substrates with the iron melt, which are performed in accordance with the sessile drop method using two different heating strategies, namely, contact and noncontact heating of metal.

Simultaneous adsorption and degradation of Zn(2+) and Cu (2+) from wastewaters using nanoscale zero-valent iron impregnated with clays.

PubMed

Shi, Li-Na; Zhou, Yan; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

2013-06-01

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu(2+) and Zn(2+) from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu(2+) and Zn(2+) from a aqueous solution containing a 100 mg/l of Cu(2+) and Zn(2+), where 92.9 % Cu(2+) and 58.3 % Zn(2+) were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu(2+) and Zn(2+). A kinetics study indicated that removing Cu(2+) and Zn(2+) with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu(2+)and Zn(2+) on bentonite and the degradation of Cu(2+)and Zn(2+) by nZVI on the bentonite. However, Cu(2+) removal by B-nZVI was reduced rather than adsorption, while Zn(2+) removal was main adsorption. Finally, Cu(2+), Zn(2+), Ni(2+), Pb(2+) and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.

Potential environmental implications of nanoscale zero-valent iron particles for environmental remediation.

PubMed

Jang, Min-Hee; Lim, Myunghee; Hwang, Yu Sik

2014-01-01

Nanoscale zero-valent iron (nZVI) particles are widely used in the field of various environmental contaminant remediation. Although the potential benefits of nZVI are considerable, there is a distinct need to identify any potential risks after environmental exposure. In this respect, we review recent studies on the environmental applications and implications of nZVI, highlighting research gaps and suggesting future research directions. Environmental application of nZVI is briefly summarized, focusing on its unique properties. Ecotoxicity of nZVI is reviewed according to type of organism, including bacteria, terrestrial organisms, and aquatic organisms. The environmental fate and transport of nZVI are also summarized with regards to exposure scenarios. Finally, the current limitations of risk determination are thoroughly provided. The ecotoxicity of nZVI depends on the composition, concentration, size and surface properties of the nanoparticles and the experimental method used, including the species investigated. In addition, the environmental fate and transport of nZVI appear to be complex and depend on the exposure duration and the exposure conditions. To date, field-scale data are limited and only short-term studies using simple exposure methods have been conducted. In this regard, the primary focus of future study should be on 1) the development of an appropriate and valid testing method of the environmental fate and ecotoxicity of reactive nanoparticles used in environmental applications and 2) assessing their potential environmental risks using in situ field scale applications.

Potential environmental implications of nanoscale zero-valent iron particles for environmental remediation

PubMed Central

Jang, Min-Hee; Lim, Myunghee; Hwang, Yu Sik

2014-01-01

Objectives Nanoscale zero-valent iron (nZVI) particles are widely used in the field of various environmental contaminant remediation. Although the potential benefits of nZVI are considerable, there is a distinct need to identify any potential risks after environmental exposure. In this respect, we review recent studies on the environmental applications and implications of nZVI, highlighting research gaps and suggesting future research directions. Methods Environmental application of nZVI is briefly summarized, focusing on its unique properties. Ecotoxicity of nZVI is reviewed according to type of organism, including bacteria, terrestrial organisms, and aquatic organisms. The environmental fate and transport of nZVI are also summarized with regards to exposure scenarios. Finally, the current limitations of risk determination are thoroughly provided. Results The ecotoxicity of nZVI depends on the composition, concentration, size and surface properties of the nanoparticles and the experimental method used, including the species investigated. In addition, the environmental fate and transport of nZVI appear to be complex and depend on the exposure duration and the exposure conditions. To date, field-scale data are limited and only short-term studies using simple exposure methods have been conducted. Conclusions In this regard, the primary focus of future study should be on 1) the development of an appropriate and valid testing method of the environmental fate and ecotoxicity of reactive nanoparticles used in environmental applications and 2) assessing their potential environmental risks using in situ field scale applications. PMID:25518840

Interphase Transformations at Metal (Copper, Iron)-Polymer Gel-Electrolyte Interfaces

NASA Astrophysics Data System (ADS)

Lyamina, G. V.; Dubinina, O. V.; Vaitulevich, E. A.; Mokrousov, G. M.

2018-07-01

The results from studies of the interface boundaries between metals (copper and iron) and gel electrolyte based on methacrylic copolymers are organized systematically. In contrast to processes in liquid electrolytes, a number of key features of the reactions that occur at such interfaces are revealed: a diffusion limiting stage; a lack of reverse reactions; and the formation of coordination compounds of metal ions with the functional groups of polymers, the stabilities of which are several orders of magnitude greater than that of coordination with their low-molecular weight counterparts. It is shown that processes which employ polymeric organogels can be used for the careful cleaning of the metal surfaces, and for the formation of a desired phase composition on the latter.

Reduction of aqueous CrVI using nanoscale zero-valent iron dispersed by high energy electron beam irradiation.

PubMed

Zhang, Jing; Zhang, Guilong; Wang, Min; Zheng, Kang; Cai, Dongqing; Wu, Zhengyan

2013-10-21

High energy electron beam (HEEB) irradiation was used to disperse nanoscale zero-valent iron (NZVI) for reduction of CrVI to CrIII in aqueous solution. Pore size distribution, scanning electron microscopy and X-ray diffraction characterizations demonstrated that HEEB irradiation could effectively increase the dispersion of NZVI resulting in more active reduction sites of Crvi on NZVI. Batch reduction experiments indicated that the reductive capacity of HEEB irradiation-modified NZVI (IMNZVI) was significantly improved, as the reductive efficiency reached 99.79% under the optimal conditions (electron beam dose of 30 kGy at 10 MeV, pH 2.0 and 313 K) compared with that of raw NZVI (72.14%). Additionally, the NZVI was stable for at least two months after irradiation. The modification mechanism of NZVI by HEEB irradiation was investigated and the results indicated that charge and thermal effects might play key roles in dispersing the NZVI particles.

Nanoscale octahedral molecular sieves: Syntheses, characterization, and applications

NASA Astrophysics Data System (ADS)

Liu, Jia

The major part of this research consists of studies on novel synthesis methods, characterization, and catalytic applications of nanoscale manganese oxide octahedral molecular sieves. The second part involves studies of new applications of bulk porous molecular sieve and layered materials (MSLM), zeolites, and inorganic powder materials for diminishing wound bleeding. Manganese oxide octahedral molecular sieves (OMS) are very important microporous materials. They have been used widely as bulk materials in catalysis, separations, chemical sensors, and batteries, due to their unique tunnel structures and useful properties. Novel methods have been developed to synthesize novel nanoscale octahedral molecular sieve manganese oxides (OMS) and metal-substituted OMS materials in order to modify their physical and chemical properties and to improve their catalytic applications. Different synthetic routes were investigated to find better, faster, and cheaper pathways to produce nanoscale or metal-substituted OMS materials. In the synthetic study of nanosize OMS materials, a combination of sol-gel synthesis and hydrothermal reaction was used to prepare pure crystalline nanofibrous todorokite-type (OMS-1) and cryptomelane-typed (OMS-2) manganese oxides using four alkali cations (Li+, K+, Na +, Rb+) and NH4+ cations. In the synthesis study of nanoscale and metal-substituted OMS materials, a combination of sol-gel synthesis and solid-state reaction was used to prepare transition metal-substituted OMS-2 nanorods, nanoneedles, and nanowires. Preparative parameters of syntheses, such as cation templates, heating temperature and time, were investigated in these syntheses of OMS-1 and OMS-2 materials. The catalytic activities of the novel synthetic nanoscale OMS materials has been evaluated on green oxidation of alcohols and toluene and were found to be much higher than their correspondent bulk materials. New applications of bulk manganese oxide molecular sieve and layered materials

Bench-scale synthesis of nanoscale materials

NASA Technical Reports Server (NTRS)

Buehler, M. F.; Darab, J. G.; Matson, D. W.; Linehan, J. C.

1994-01-01

A novel flow-through hydrothermal method used to synthesize nanoscale powders is introduced by Pacific Northwest Laboratory. The process, Rapid Thermal Decomposition of precursors in Solution (RTDS), uniquely combines high-pressure and high-temperature conditions to rapidly form nanoscale particles. The RTDS process was initially demonstrated on a laboratory scale and was subsequently scaled up to accommodate production rates attractive to industry. The process is able to produce a wide variety of metal oxides and oxyhydroxides. The powders are characterized by scanning and transmission electron microscopic methods, surface-area measurements, and x-ray diffraction. Typical crystallite sizes are less than 20 nanometers, with BET surface areas ranging from 100 to 400 sq m/g. A description of the RTDS process is presented along with powder characterization results. In addition, data on the sintering of nanoscale ZrO2 produced by RTDS are included.

The removal of uranium onto carbon-supported nanoscale zero-valent iron particles

NASA Astrophysics Data System (ADS)

Crane, Richard A.; Scott, Thomas

2014-12-01

In the current work carbon-supported nanoscale zero-valent iron particles (CS nZVI), synthesised by the vacuum heat treatment of ferric citrate trihydrate absorbed onto carbon black, have been tested for the removal of uranium (U) from natural and synthetic waters. Two types of CS nZVI were tested, one vacuum annealed at 600 °C for 4 h and the other vacuum annealed at 700 °C for 4 h, with their U removal behaviour compared to nZVI synthesised via the reduction of ferrous iron using sodium borohydride. The batch systems were analysed over a 28-day reaction period during which the liquid and nanoparticulate solids were periodically analysed to determine chemical evolution of the solutions and particulates. Results demonstrate a well-defined difference between the two types of CS nZVI, with greater U removal exhibited by the nanomaterial synthesised at 700 °C. The mechanism has been attributed to the CS nZVI synthesised at 700 °C exhibiting (i) a greater proportion of surface oxide Fe2+ to Fe3+ (0.34 compared to 0.28); (ii) a greater conversion of ferric citrate trihydrate [2Fe(C6H5O7)·H2O] to Fe0; and (iii) a larger surface area (108.67 compared to 88.61 m2 g-1). Lower maximum U uptake was recorded for both types of CS nZVI in comparison with the borohydride-reduced nZVI. A lower decrease in solution Eh and DO was also recorded, indicating that less chemical reduction of U was achieved by the CS nZVI. Despite this, lower U desorption in the latter stages of the experiment (>7 days) was recorded for the CS nZVI synthesised at 700 °C, indicating that carbon black in the CS nZVI is likely to have contributed towards U sorption and retention. Overall, it can be stated that the borohydride-reduced nZVI were significantly more effective than CS nZVI for U removal over relatively short timescales (e.g. <48 h), however, they were more susceptible to U desorption over extended time periods.

Hybrid zero valent iron (ZVI)/H2O2 oxidation process for landfill leachate treatment with novel nanosize metallic calcium/iron composite.

PubMed

Lee, Son Dong; Mallampati, Srinivasa Reddy; Lee, Byoung Ho

2017-04-01

A novel nanosize metallic calcium/iron dispersed reagent was synthesized and tested as coagulant/catalyst in a hybrid zero valent iron (ZVI)/H 2 O 2 oxidation process to treat leachate. Two different types of leachates, one from municipal solid waste (MSW) tipping hall (MSWIL) and second from an MSW landfill site (MSWLL), were collected and characterized. The morphology, elemental composition, and mineral phases of the nano-Ca/CaO and nano-Fe/Ca/CaO were characterized by scanning electron microscopy-electron dispersive spectroscopy (SEM-EDS) and x-ray powder diffraction (XRD) analysis. The coagulation process with 2.5 g L -1 nano-Ca/CaO attained 64.0, 56.0, and 20.7% removal of color, chemical oxygen demand (COD), and total suspended solids (TSS) in MSWLL. With only 1.0 g L -1 of nano-Fe/Ca/CaO, relatively high color, COD and TSS removal was achieved in MSWLL at 67.5, 60.2, and 37.7%, respectively. The heavy metal removal efficiency reached 91-99% after treatment with nano-Fe/Ca/CaO in both leachate samples. The coupling process, using 1.0 g L -1 of nano-Fe/Ca/CaO and 20 mM H 2 O 2 doses, achieved enhancement removal of color, COD, and TSS, up to 95%, 96%, and 66%, respectively, without initial pH control. After this treatment, the color, COD, TSS, and heavy metals were significantly decreased, fitting the Korean discharge regulation limit. A hybrid coupled zero valent iron (ZVI)/H 2 O 2 oxidation process with novel nanosized metallic calcium/iron dispersed reagent proved to be a suitable treatment for dealing with leachate samples. Conventional treatments (biological or physicochemical) are not sufficient anymore to reach the level of purification needed to fully reduce the negative impact of landfill leachates on the environment. This implies that new treatment alternatives species must be proposed. A coupled zero valent iron (ZVI)/H 2 O 2 oxidation process proved to be a suitable treatment for dealing with leachate samples. Coagulation with nFe/Ca/CaO allows 91

Electromagnetic Induction of Zerovalent Iron (ZVI) Powder and Nanoscale Zerovalent Iron (NZVI) Particles Enhances Dechlorination of Trichloroethylene in Contaminated Groundwater and Soil: Proof of Concept.

PubMed

Phenrat, Tanapon; Thongboot, Thippawan; Lowry, Gregory V

2016-01-19

This study evaluates the concept of using zerovalent iron (ZVI) powder or nanoscale zerovalent iron (NZVI) particles in combination with a low frequency (150 kHz) AC electromagnetic field (AC EMF) to effectively remove trichloroethylene (TCE) from groundwater and saturated soils. ZVI and NZVI are ferromagnetic, which can induce heat under applied AC EMF. The heat generated by ZVI and NZVI induction can increase the rate of dechlorination, according to Arrhenius' equation, and increase the rate of TCE desorption from TCE-sorbed soil. Both dechlorination and TCE desorption enhance the overall TCE removal rate. We evaluated this novel concept in laboratory batch reactors. We found that both ZVI and NZVI can induce heat under applied AC EMF up to 120 °C in 20 min. Using ZVI and NZVI with AC EMF enhanced dechlorination of dissolved TCE (no soil) up to 4.96-fold. In addition to increasing the temperature by ZVI and NZVI induction heating, AC EMF increased intrinsic ZVI and NZVI reactivity, ostensibly due to accelerated corrosion, as demonstrated by the increased ORP. In a soil-water-TCE system, NZVI together with AC EMF thermally enhanced desorption of TCE from soil and increased the degradation of TCE up to 5.36-fold compared to the absence of AC EMF. For the first time, this study indicates the potential for ZVI and NZVI coupled with AC EMF as a combined remediation technique for increasing the rate and completeness of in situ cleanup of adsorbed phase contaminants.

Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: reactivity, characterization and mechanism.

PubMed

Zhang, Xin; Lin, Shen; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

2011-05-01

The use of nanoscale zero-valent iron (nZVI) to remediate contaminated groundwater is limited due to its lack of durability and mechanical strength. To address this issue, 20% (w/w) nZVI was loaded onto kaolinite as a support material (K-nZVI). More than 96% of Pb(2+) was removed from aqueous solution using K-nZVI at an initial condition of 500 mg/L Pb(2+) within 30 min under the conditions of 10 g/L of K-nZVI, pH 5.10 and a temperature of 30 °C. To understand the mechanism of removal of Pb(2+), various techniques were implemented to characterize K-nZVI. Scanning electron microscopy (SEM) indicated that K-nZVI had a suitable dispersive state with a lower aggregation, where the mean specific surface area and average particle size as determined by the BET-N(2) method and X-ray diffraction (XRD), were 26.11 m(2)/g and 44.3 nm, respectively. The results obtained from XRD, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) indicated that a small number of iron oxides formed on the surface of K-nZVI, suggesting that free Pb(2+) was adsorbed onto K-nZVI and subsequently reduced to Pb(0). Copyright © 2011 Elsevier Ltd. All rights reserved.

The challenge of screen printed Ag metallization on nano-scale poly-silicon passivated contacts for silicon solar cells

NASA Astrophysics Data System (ADS)

Jiang, Lin; Song, Lixin; Yan, Li; Becht, Gregory; Zhang, Yi; Hoerteis, Matthias

2017-08-01

Passivated contacts can be used to reduce metal-induced recombination for higher energy conversion efficiency for silicon solar cells, and are obtained increasing attentions by PV industries in recent years. The reported thicknesses of passivated contact layers are mostly within tens of nanometer range, and the corresponding metallization methods are realized mainly by plating/evaporation technology. This high cost metallization cannot compete with the screen printing technology, and may affect its market potential comparing with the presently dominant solar cell technology. Very few works have been reported on screen printing metallization on passivated contact solar cells. Hence, there is a rising demand to realize screen printing metallization technology on this topic. In this work, we investigate applying screen printing metallization pastes on poly-silicon passivated contacts. The critical challenge for us is to build low contact resistance that can be competitive to standard technology while restricting the paste penetrations within the thin nano-scale passivated contact layers. The contact resistivity of 1.1mohm-cm2 and the open circuit voltages > 660mV are achieved, and the most appropriate thickness range is estimated to be around 80 150nm.

Charge transport in nanoscale "all-inorganic" networks of semiconductor nanorods linked by metal domains.

PubMed

Lavieville, Romain; Zhang, Yang; Casu, Alberto; Genovese, Alessandro; Manna, Liberato; Di Fabrizio, Enzo; Krahne, Roman

2012-04-24

Charge transport across metal-semiconductor interfaces at the nanoscale is a crucial issue in nanoelectronics. Chains of semiconductor nanorods linked by Au particles represent an ideal model system in this respect, because the metal-semiconductor interface is an intrinsic feature of the nanosystem and does not manifest solely as the contact to the macroscopic external electrodes. Here we investigate charge transport mechanisms in all-inorganic hybrid metal-semiconductor networks fabricated via self-assembly in solution, in which CdSe nanorods were linked to each other by Au nanoparticles. Thermal annealing of our devices changed the morphology of the networks and resulted in the removal of small Au domains that were present on the lateral nanorod facets, and in ripening of the Au nanoparticles in the nanorod junctions with more homogeneous metal-semiconductor interfaces. In such thermally annealed devices the voltage dependence of the current at room temperature can be well described by a Schottky barrier lowering at a metal semiconductor contact under reverse bias, if the spherical shape of the gold nanoparticles is considered. In this case the natural logarithm of the current does not follow the square-root dependence of the voltage as in the bulk, but that of V(2/3). From our fitting with this model we extract the effective permittivity that agrees well with theoretical predictions for the permittivity near the surface of CdSe nanorods. Furthermore, the annealing improved the network conductance at cryogenic temperatures, which could be related to the reduction of the number of trap states.

Mechanisms and efficiency of the simultaneous removal of metals and cyanides by using ferrate(VI): crucial roles of nanocrystalline iron(III) oxyhydroxides and metal carbonates.

PubMed

Filip, Jan; Yngard, Ria A; Siskova, Karolina; Marusak, Zdenek; Ettler, Vojtech; Sajdl, Petr; Sharma, Virender K; Zboril, Radek

2011-08-29

The reaction of potassium ferrate(VI), K(2)FeO(4), with weak-acid dissociable cyanides--namely, K(2)[Zn(CN)(4)], K(2)[Cd(CN)(4)], K(2)[Ni(CN)(4)], and K(3)[Cu(CN)(4)]--results in the formation of iron(III) oxyhydroxide nanoparticles that differ in size, crystal structure, and surface area. During cyanide oxidation and the simultaneous reduction of iron(VI), zinc(II), copper(II), and cadmium(II), metallic ions are almost completely removed from solution due to their coprecipitation with the iron(III) oxyhydroxides including 2-line ferrihydrite, 7-line ferrihydrite, and/or goethite. Based on the results of XRD, Mössbauer and IR spectroscopies, as well as TEM, X-ray photoelectron emission spectroscopy, and Brunauer-Emmett-Teller measurements, we suggest three scavenging mechanisms for the removal of metals including their incorporation into the ferrihydrite crystal structure, the formation of a separate phase, and their adsorption onto the precipitate surface. Zn and Cu are preferentially and almost completely incorporated into the crystal structure of the iron(III) oxyhydroxides; the formation of the Cd-bearing, X-ray amorphous phase, together with Cd carbonate is the principal mechanism of Cd removal. Interestingly, Ni remains predominantly in solution due to the key role of nickel(II) carbonate, which exhibits a solubility product constant several orders of magnitude higher than the carbonates of the other metals. Traces of Ni, identified in the iron(III) precipitate, are exclusively adsorbed onto the large surface area of nanoparticles. We discuss the relationship between the crystal structure of iron(III) oxyhydroxides and the mechanism of metal removal, as well as the linear relationship observed between the rate constant and the surface area of precipitates. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Imaging of Light-Matter Coupling Inside Metal-Coated Cavities with a Pulsed Electron Beam.

PubMed

Moerland, Robert J; Weppelman, I Gerward C; Scotuzzi, Marijke; Hoogenboom, Jacob P

2018-05-02

Many applications in (quantum) nanophotonics rely on controlling light-matter interaction through strong, nanoscale modification of the local density of states (LDOS). All-optical techniques probing emission dynamics in active media are commonly used to measure the LDOS and benchmark experimental performance against theoretical predictions. However, metal coatings needed to obtain strong LDOS modifications in, for instance, nanocavities, are incompatible with all-optical characterization. So far, no reliable method exists to validate theoretical predictions. Here, we use subnanosecond pulses of focused electrons to penetrate the metal and excite a buried active medium at precisely defined locations inside subwavelength resonant nanocavities. We reveal the spatial layout of the spontaneous-emission decay dynamics inside the cavities with deep-subwavelength detail, directly mapping the LDOS. We show that emission enhancement converts to inhibition despite an increased number of modes, emphasizing the critical role of optimal emitter location. Our approach yields fundamental insight in dynamics at deep-subwavelength scales for a wide range of nano-optical systems.

Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening

PubMed Central

Comtet, Jean; Niguès, Antoine; Kaiser, Vojtech; Coasne, Benoit; Bocquet, Lydéric; Siria, Alessandro

2017-01-01

Room temperature Ionic liquids (RTIL) are new materials with fundamental importance for energy storage and active lubrication. They are unsual liquids, which challenge the classical frameworks of electrolytes, whose behavior at electrified interfaces remains elusive with exotic responses relevant to their electrochemical activity. By means of tuning fork based AFM nanorheological measurements, we explore here the properties of confined RTIL, unveiling a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to capillary freezing in confinement. This threshold is related to the metallic nature of the confining materials, with more metallic surfaces facilitating freezing. This is interpreted in terms of the shift of freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces. Our findings provide fresh views on the properties of confined RTIL with implications for their properties inside nanoporous metallic structures and suggests applications to tune nanoscale lubrication with phase-changing RTIL, by varying the nature and patterning of the substrate, and application of active polarisation. PMID:28346432

Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening

NASA Astrophysics Data System (ADS)

Comtet, Jean; Niguès, Antoine; Kaiser, Vojtech; Coasne, Benoit; Bocquet, Lydéric; Siria, Alessandro

2017-06-01

Room-temperature ionic liquids (RTILs) are new materials with fundamental importance for energy storage and active lubrication. They are unusual liquids, which challenge the classical frameworks of electrolytes, whose behaviour at electrified interfaces remains elusive, with exotic responses relevant to their electrochemical activity. Using tuning-fork-based atomic force microscope nanorheological measurements, we explore here the properties of confined RTILs, unveiling a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to capillary freezing in confinement. This threshold is related to the metallic nature of the confining materials, with more metallic surfaces facilitating freezing. This behaviour is interpreted in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces. Our findings provide fresh views on the properties of confined RTIL with implications for their properties inside nanoporous metallic structures, and suggests applications to tune nanoscale lubrication with phase-changing RTILs, by varying the nature and patterning of the substrate, and application of active polarization.

Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening.

PubMed

Comtet, Jean; Niguès, Antoine; Kaiser, Vojtech; Coasne, Benoit; Bocquet, Lydéric; Siria, Alessandro

2017-06-01

Room-temperature ionic liquids (RTILs) are new materials with fundamental importance for energy storage and active lubrication. They are unusual liquids, which challenge the classical frameworks of electrolytes, whose behaviour at electrified interfaces remains elusive, with exotic responses relevant to their electrochemical activity. Using tuning-fork-based atomic force microscope nanorheological measurements, we explore here the properties of confined RTILs, unveiling a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to capillary freezing in confinement. This threshold is related to the metallic nature of the confining materials, with more metallic surfaces facilitating freezing. This behaviour is interpreted in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces. Our findings provide fresh views on the properties of confined RTIL with implications for their properties inside nanoporous metallic structures, and suggests applications to tune nanoscale lubrication with phase-changing RTILs, by varying the nature and patterning of the substrate, and application of active polarization.

Heavy Metals Induce Iron Deficiency Responses at Different Hierarchic and Regulatory Levels.

PubMed

Lešková, Alexandra; Giehl, Ricardo F H; Hartmann, Anja; Fargašová, Agáta; von Wirén, Nicolaus

2017-07-01

In plants, the excess of several heavy metals mimics iron (Fe) deficiency-induced chlorosis, indicating a disturbance in Fe homeostasis. To examine the level at which heavy metals interfere with Fe deficiency responses, we carried out an in-depth characterization of Fe-related physiological, regulatory, and morphological responses in Arabidopsis ( Arabidopsis thaliana ) exposed to heavy metals. Enhanced zinc (Zn) uptake closely mimicked Fe deficiency by leading to low chlorophyll but high ferric-chelate reductase activity and coumarin release. These responses were not caused by Zn-inhibited Fe uptake via IRON-REGULATED TRANSPORTER (IRT1). Instead, Zn simulated the transcriptional response of typical Fe-regulated genes, indicating that Zn affects Fe homeostasis at the level of Fe sensing. Excess supplies of cobalt and nickel altered root traits in a different way from Fe deficiency, inducing only transient Fe deficiency responses, which were characterized by a lack of induction of the ethylene pathway. Cadmium showed a rather inconsistent influence on Fe deficiency responses at multiple levels. By contrast, manganese evoked weak Fe deficiency responses in wild-type plants but strongly exacerbated chlorosis in irt1 plants, indicating that manganese antagonized Fe mainly at the level of transport. These results show that the investigated heavy metals modulate Fe deficiency responses at different hierarchic and regulatory levels and that the interaction of metals with physiological and morphological Fe deficiency responses is uncoupled. Thus, this study not only emphasizes the importance of assessing heavy metal toxicities at multiple levels but also provides a new perspective on how Fe deficiency contributes to the toxic action of individual heavy metals. © 2017 American Society of Plant Biologists. All Rights Reserved.

Novel synthesis of carbon spheres supported nanoscale zero-valent iron for removal of metronidazole

NASA Astrophysics Data System (ADS)

Wang, Xiangyu; Du, Yi; Ma, Jun

2016-12-01

For the first time, carbon spheres-supported nanoscale zero-valent iron (NZVI/CSs) were successfully synthesized as functionalized composite via liquid phase reduction method and adopted for removal of a typical antibiotic, metronidazole (MNZ), from wastewater. The resultant composite (NZVI/CSs) exhibit higher reactivity, excellent stability, enhanced dispersion, and improved longevity over the reaction course due to the presence of the charged carboxyl groups and hydroxyl groups on the surfaces of CSs. The results show that 94.18% of MNZ was removed using NZVI/CSs after 6 min, while only 36.45% and 8.78% of MNZ were removed using NZVI and CSs, respectively. The galvanic cell system between NZVI and CSs was essential for enhancing MNZ reduction in aqueous solution. Furthermore, the new findings include kinetics for MNZ removal by NZVI/CSs composite could be well expressed by a revised two-parameter pseudo-first-order model. Finally, the possible degradation mechanism was proposed, which was based on the analysis of degraded products by high performance liquid chromatography-mass spectrometry (HPLC-MS). Different important factors impacting on MNZ removal (including mass ratio of NZVI to CSs, initial concentration, pH value and solution temperature) were investigated as well. Overall, this study provides a promising alternative material and environmental pollution management option for antibiotic wastewater treatment.

Degradation of bromamine acid by nanoscale zero-valent iron (nZVI) supported on sepiolite.

PubMed

Fei, Xuening; Cao, Lingyun; Zhou, Lifeng; Gu, Yingchun; Wang, Xiaoyang

2012-01-01

Sepiolite, a natural nano-material, was chosen as a carrier to prepare supported nanoscale zero-valent iron (nZVI). The effects of preparation conditions, including mass ratio of nZVI and activated sepiolite and preparation pH value, on properties of the supported nZVI were investigated. The results showed that the optimal mass ratio of nZVI and sepiolite was 1.12:1 and the optimal pH value was 7. The supported nZVI was characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and energy dispersive spectrometer (EDS), and furthermore an analogy model of the supported nZVI was set up. Compared with the nZVI itself, the supported nZVI was more stable in air and possessed better water dispersibility, which were beneficial for the degradation of bromamine acid aqueous solution. The degradation characteristics, such as effects of supported nZVI dosage, initial concentration and initial pH value of the solution on the decolorization efficiency were also investigated. The results showed that in an acidic environment the supported nZVI with a dosage of 2 g/L showed high activity in the degradation of bromamine acid with an initial concentration of 1,000 mg/L, and the degree of decolorization could reach up to 98%.

Trace metals related to historical iron smelting at Hopewell Furnace National Historic Site, Berks and Chester Counties, Pennsylvania

USGS Publications Warehouse

Sloto, Ronald A.

2011-01-01

Iron ore containing elevated concentrations of trace metals was smelted at Hopewell Furnace during its 113 years of operation (1771-1883). The ore used at Hopewell Furnace was obtained from iron mines within 5 miles of the furnace. The iron-ore deposits were formed about 200 million years ago and contain abundant magnetite, the primary iron mineral, and accessory minerals enriched in arsenic, cobalt, copper, lead, and other metals. Hopewell Furnace, built by Mark Bird during 1770-71, was one of the last of the charcoal-burning, cold-blast iron furnaces operated in Pennsylvania. The most productive years for Hopewell Furnace were from 1830 to 1837. Castings were the most profitable product, especially the popular Hopewell Stove. More than 80,000 stoves were cast at Hopewell, which produced as many as 23 types and sizes of cooking and heating stoves. Beginning in the 1840s, the iron industry shifted to large-scale, steam-driven coke and anthracite furnaces. Independent rural enterprises like Hopewell could no longer compete when the iron and steel industries consolidated in urban manufacturing centers. The furnace ceased operation in 1883 (Kurjack, 1954). The U.S. Geological Survey (USGS), in cooperation with the National Park Service, completed a study at Hopewell Furnace National Historic Site (NHS) in Berks and Chester Counties, Pennsylvania, to determine the fate of toxic trace metals, such as arsenic, cobalt, and lead, released into the environment during historical iron-smelting operations. The results of the study, conducted during 2008-10, are presented in this fact sheet.

Immobilization of heavy metals in electroplating sludge by biochar and iron sulfide.

PubMed

Lyu, Honghong; Gong, Yanyan; Tang, Jingcshun; Huang, Yao; Wang, Qilin

2016-07-01

Electroplating sludge (ES) containing large quantities of heavy metals is regarded as a hazardous waste in China. This paper introduced a simple method of treating ES using environmentally friendly fixatives biochar (BC) and iron sulfide (FeS), respectively. After 3 days of treatment with FeS at a FeS-to-ES mass ratio of 1:5, the toxicity characteristic leaching procedure (TCLP)-based leachability of total Cr (TCr), Cu(II), Ni(II), Pb(II), and Zn(II) was decreased by 59.6, 100, 63.8, 73.5, and 90.5 %, respectively. After 5 days of treatment with BC at a BC-to-ES mass ratio of 1:2, the TCLP-based leachability was declined by 35.1, 30.6, 22.3, 23.1, and 22.4 %, respectively. Pseudo first-order kinetic model adequately simulated the sorption kinetic data. Structure and morphology analysis showed that adsorption, electrostatic attraction, surface complexation, and chemical precipitation were dominant mechanisms for heavy metals immobilization by BC, and that chemical precipitation (formation of metal sulfide and hydroxide precipitates), iron exchange (formation of CuFeS2), and surface complexation were mainly responsible for heavy metals removal by FeS. Economic costs of BC and FeS were 500 and 768 CNY/t, lower than that of Na2S (940 CNY/t). The results suggest that BC and FeS are effective, economic, and environmentally friendly fixatives for immobilization of heavy metals in ES before landfill disposal.

Carbon Solubility in Silicon-Iron-Bearing Metals during Core Formation on Mercury

NASA Technical Reports Server (NTRS)

Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Ross, D. Kent; Rapp, Jennifer F.; Danielson, Lisa R.; Keller, Lindsay P.; Righter, Kevin

2016-01-01

Recent results obtained from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft showed the surface of Mercury has high S abundances (approximately 4 wt%) and low Iron(II) Oxide abundances (less than 2 wt%). Based on these extreme values, the oxygen fugacity of Mercury's surface materials was estimated to be approximately 3 to 7 log(sub 10) units below the IW buffer (Delta IW-3 to Delta IW-7). This highly reducing nature of the planet has resulted in a large core and relatively thin mantle, extending to only approximately 420 km depth (corresponding to a core-mantle boundary pressure of approximately 4-7 GPa) within the planet. Furthermore, MESSENGER results have suggested the presence of carbon on the surface of the planet. Previous experimental results from have also suggested the possibility of a primary floatation crust on Mercury composed of graphite, produced after a global magma ocean event. With these exotic conditions of this compositional end-member planet, it begs the question, what is the core composition of Mercury? Although no definitive conclusion has been reached, previous studies have made advances towards answering this question. Riner et al. and Chen et al. looked at iron sulfide systems and implemented various crystallization and layered core scenarios to try and determine the composition and structure of Mercury's core. Malavergne et al. examined core crystallization scenarios in the presence of sulfur and silicon. Hauck et al. used the most recent geophysical constraints from the MESSENGER spacecraft to model the internal structure of Mercury, including the core, in a iron-sulfur-silicon system. More recently, Chabot et al. conducted a series of metal-silicate partitioning experiments in a iron-sulfur-silicon system. These results showed the core of Mercury has the potential to contain more than 15 wt% silicon. However, with the newest results from MESSENGER's low altitude campaign, carbon is another

Metallic iron for water treatment: leaving the valley of confusion

NASA Astrophysics Data System (ADS)

Makota, Susanne; Nde-Tchoupe, Arnaud I.; Mwakabona, Hezron T.; Tepong-Tsindé, Raoul; Noubactep, Chicgoua; Nassi, Achille; Njau, Karoli N.

2017-12-01

Researchers on metallic iron (Fe0) for environmental remediation and water treatment are walking in a valley of confusion for 25 years. This valley is characterized by the propagation of different beliefs that have resulted from a partial analysis of the Fe0/H2O system as (1) a reductive chemical reaction was considered an electrochemical one and (2) the mass balance of iron has not been really addressed. The partial analysis in turn has been undermining the scientific method while discouraging any real critical argumentation. This communication re-establishes the complex nature of the Fe0/H2O system while recalling that, finally, proper system analysis and chemical thermodynamics are the most confident ways to solve any conflicting situation in Fe0 environmental remediation.

Effects of thermomechanical processing on strength and toughness of iron - 12-percent-nickel - reactive metal alloys at -196 C

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1978-01-01

Thermomechanical processing (TMP) was evaluated as a method of strengthening normally tough iron-12-nickel-reactive metal alloys at cryogenic temperatures. Five iron-12 nickel alloys with reactive metal additions of aluminum, niobium, titanium, vanadium, and aluminum plus niobium were investigated. Primary evaluation was based on the yield strength and fracture toughness of the thermomechanically processed alloys at -196 C.

Active catalysts of sonoelectrochemically prepared iron metal nanoparticles for the electroreduction of chloroacetates

NASA Astrophysics Data System (ADS)

Sáez, V.; González-García, J.; Marken, F.

2010-01-01

A new methodology for the sonoelectro-deposition and stripping of highly reactive iron at boron-doped diamond electrodes has been studied. In aqueous 1 M NH4F iron metal readily and reversibly electro-deposits onto boron-doped diamond electrodes. The effects of deposition potential, FeF63- concentration, deposition time, and mass transport are investigated and also the influence of power ultrasound (24 kHz, 8 Wcm-2). Scanning electron microscopy images of iron nanoparticles grown to typically 20-30 nm diameters are obtained. It is shown that a strongly and permanently adhering film of iron at boron-doped diamond can be formed and transferred into other solution environments. The catalytic reactivity of iron deposits at boron-doped diamond is investigated for the reductive dehalogenation of chloroacetate. The kinetically limited multi-electron reduction of trichloroacetate is dependent on the FeF63- deposition conditions and the solution composition. It is demonstrated that a stepwise iron-catalysed dechlorination via dichloroacetate and monochloroacetate to acetate is feasible. This sonoelectrochemical methodology offers a novel, clean and very versatile electro-dehalogenation methodology. The role of fluoride in the surface electrochemistry of iron deserves further attention.

Sources and fates of heavy metals in a mining-impacted stream: Temporal variability and the role of iron oxides

PubMed Central

Schaider, Laurel A.; Senn, David B.; Estes, Emily R.; Brabander, Daniel J.; Shine, James P.

2014-01-01

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal: mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 μg g−1), Pb (up to 550 μg g−1) and Cd (up to 200 μg g−1) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage. PMID:24867708

Red mud (RM)-Induced enhancement of iron plaque formation reduces arsenic and metal accumulation in two wetland plant species.

PubMed

Yang, J X; Guo, Q J; Yang, J; Zhou, X Y; Ren, H Y; Zhang, H Z; Xu, R X; Wang, X D; Peters, M; Zhu, G X; Wei, R F; Tian, L Y; Han, X K

2016-01-01

Human activities have resulted in arsenic (As) and heavy metals accumulation in paddy soils in China. Phytoremediation has been suggested as an effective and low-cost method to clean up contaminated soils. A combined soil-sand pot experiment was conducted to investigate the influence of red mud (RM) supply on iron plaque formation and As and heavy metal accumulation in two wetland plant species (Cyperus alternifolius Rottb., Echinodorus amazonicus Rataj), using As and heavy metals polluted paddy soil combined with three rates of RM application (0, 2%, 5%). The results showed that RM supply significantly decreased As and heavy metals accumulation in shoots of the two plants due to the decrease of As and heavy metal availability and the enhancement of the formation of iron plaque on the root surface and in the rhizosphere. Both wetland plants supplied with RM tended to have more Fe plaque, higher As and heavy metals on roots and in their rhizospheres, and were more tolerant of As and heavy metal toxicity. The results suggest that RM-induced enhancement of the formation of iron plaque on the root surface and in the rhizosphere of wetland plants may be significant for remediation of soils contaminated with As and heavy metals.

Iron-targeting antitumor activity of gallium compounds and novel insights into triapine(®)-metal complexes.

PubMed

Chitambar, Christopher R; Antholine, William E

2013-03-10

Despite advances made in the treatment of cancer, a significant number of patients succumb to this disease every year. Hence, there is a great need to develop new anticancer agents. Emerging data show that malignant cells have a greater requirement for iron than normal cells do and that proteins involved in iron import, export, and storage may be altered in cancer cells. Therefore, strategies to perturb these iron-dependent steps in malignant cells hold promise for the treatment of cancer. Recent studies show that gallium compounds and metal-thiosemicarbazone complexes inhibit tumor cell growth by targeting iron homeostasis, including iron-dependent ribonucleotide reductase. Chemical similarities of gallium(III) with iron(III) enable the former to mimic the latter and interpose itself in critical iron-dependent steps in cellular proliferation. Newer gallium compounds have emerged with additional mechanisms of action. In clinical trials, the first-generation-compound gallium nitrate has exhibited activity against bladder cancer and non-Hodgkin's lymphoma, while the thiosemicarbazone Triapine(®) has demonstrated activity against other tumors. Novel gallium compounds with greater cytotoxicity and a broader spectrum of antineoplastic activity than gallium nitrate should continue to be developed. The antineoplastic activity and toxicity of the existing novel gallium compounds and thiosemicarbazone-metal complexes should be tested in animal tumor models and advanced to Phase I and II clinical trials. Future research should identify biologic markers that predict tumor sensitivity to gallium compounds. This will help direct gallium-based therapy to cancer patients who are most likely to benefit from it.

Removal of polybrominated diphenyl ethers by biomass carbon-supported nanoscale zerovalent iron particles: influencing factors, kinetics, and mechanism.

PubMed

Fu, Rongbing; Xu, Zhen; Peng, Lin; Bi, Dongsu

2016-12-01

In this study, nanoscale zerovalent iron (NZVI) immobilized on biomass carbon was used for the high efficient removal of BDE 209. NZVI supported on biomass carbon minimized the aggregation of NZVI particles resulting in the increased reaction performance. The proposed removal mechanism included the adsorption of BDE 209 on the surface or interior of the biomass carbon NZVI (BC-NZVI) particles and the subsequent debromination of BDE 209 by NZVI while biomass carbon served as an electron shuttle. BC-NZVI particles and the interaction between BC-NZVI particles and BDE 209 were characterized by TEM, XRD, and XPS. The removal reaction followed a pseudo-first-order rate expression under different reaction conditions, and the k obs was higher than that of other NZVI-supported materials. The debromination of BDE 209 by BC-NZVI was a stepwise process from nona-BDE to DE. A proposed pathway suggested that supporting NZVI on biomass carbon has potential as a promising technique for in situ organic-contaminated groundwater remediation.

Nitrogen activation of carbon-encapsulated zero-valent iron nanoparticles and influence of the activation temperature on heavy metals removal

NASA Astrophysics Data System (ADS)

Bonaiti, Stefania; Calderon, Blanca; Collina, Elena; Lasagni, Marina; Mezzanotte, Valeria; Aracil, Ignacio; Fullana, Andrés

2017-05-01

Nanoparticles of zero-valent iron (nZVI) represent a promising agent for environmental remediation. This is due to their core-shell structure which presents the characteristics of both metallic and oxidised iron, leading to sorption and reductive precipitation of metal ions. Nevertheless, nZVI application presents some limitations regarding their rapid oxidation and aggregation in the media which leads to the delivery of the ions after some hours (the “aging effect”). To address these issues, modifications of nZVI structure and synthesis methods have been developed in the last years. The aging problem was solved by using nZVI encapsulated inside carbon spheres (CE-nZVI), synthetized through Hydrothermal Carbonization (HTC). Results showed high heavy metals removal percentage. Furthermore, CE-nZVI were activated with nitrogen in order to increase the metallic iron content. The aim of this study was to test CE-nZVI post-treated with nitrogen at different temperatures in heavy metals removal, demonstrating that the influence of the temperature was negligible in nanoparticles removal efficiency.

Dielectric Metasurface as a Platform for Spatial Mode Conversion in Nanoscale Waveguides.

PubMed

Ohana, David; Desiatov, Boris; Mazurski, Noa; Levy, Uriel

2016-12-14

We experimentally demonstrate a nanoscale mode converter that performs coupling between the first two transverse electric-like modes of a silicon-on-insulator waveguide. The device operates by introducing a nanoscale periodic perturbation in its effective refractive index along the propagation direction and a graded effective index profile along its transverse direction. The periodic perturbation provides phase matching between the modes, while the graded index profile, which is realized by the implementation of nanoscale dielectric metasurface consisting of silicon features that are etched into the waveguide taking advantage of the effective medium concept, provides the overlap between the modes. Following the device design and numerical analysis using three-dimensional finite difference time domain simulations, we have fabricated the device and characterized it by directly measuring the modal content using optical imaging microscopy. From these measurements, the mode purity is estimated to be 95% and the transmission relative to an unperturbed strip waveguide is as high as 88%. Finally, we extend this approach to accommodate for the coupling between photonic and plasmonic modes. Specifically, we design and numerically demonstrate photonic to plasmonic mode conversion in a hybrid waveguide in which photonic and surface plasmon polariton modes can be guided in the silicon core and in the silicon/metal interface, respectively. The same method can also be used for coupling between symmetric and antisymmetric plasmonic modes in metal-insulator-metal or insulator-metal-insulator structures. On the basis of the current demonstration, we believe that such nanoscale dielectric metasurface-based mode converters can now be realized and become an important building block in future nanoscale photonic and plasmonic devices. Furthermore, the demonstrated platform can be used for the implementation of other chip scale components such as splitters, combiners couplers, and more.

[Effect of the change in sulphate and dissolved oxygen mass concentration on metal release in old cast iron distribution pipes].

PubMed

Wu, Yong-li; Shi, Bao-you; Sun, Hui-fang; Zhang, Zhi-huan; Gu, Jun-nong; Wang, Dong-sheng

2013-09-01

To understand the processes of corrosion by-product release and the consequent "red water" problems caused by the variation of water chemical composition in drinking water distribution system, the effect of sulphate and dissolved oxygen (DO) concentration on total iron release in corroded old iron pipe sections historically transporting groundwater was investigated in laboratory using small-scale pipe section reactors. The release behaviors of some low-level metals, such as Mn, As, Cr, Cu, Zn and Ni, in the process of iron release were also monitored. The results showed that the total iron and Mn release increased significantly with the increase of sulphate concentration, and apparent red water occurred when sulphate concentration was above 400 mg x L(-1). With the increase of sulfate concentration, the effluent concentrations of As, Cr, Cu, Zn and Ni also increased obviously, however, the effluent concentrations of these metals were lower than the influent concentrations under most circumstances, which indicated that adsorption of these metals by pipe corrosion scales occurred. Increasing DO within a certain range could significantly inhibit the iron release.

Nanoscale Zero-Valent Iron (NZVI) supported on sineguelas waste for Pb(II) removal from aqueous solution: kinetics, thermodynamic and mechanism.

PubMed

Arshadi, M; Soleymanzadeh, M; Salvacion, J W L; SalimiVahid, F

2014-07-15

In this study, the synthesis and characterization of a new adsorbent containing nanoscale zerovalent iron particles (NZVI) decorated sineguelas waste (S-NaOH-NZVI) from agriculture biomass was investigated for the adsorption/reduction of inorganic pollution such as Pb(II) ions. The combination of ZVI particles on the surface of sineguelas waste can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. The synthesized materials were characterized with different methods such as FT-IR, BET, XRD, TEM and pHPZC. Good dispersion of NZVI particles (ca. 10-70nm) on the sineguelas waste was observed. The effects of various parameters, such as contact time, pH, concentration, adsorbent dosage and temperature were studied. The adsorption of Pb(II) ions has been studied in terms of pseudo-first- and second-order kinetics, and the Freundlich, Langmuir and Langmuir-Freundlich isotherms models have also been used to the equilibrium adsorption data. The adsorption kinetics followed the mechanism of the pseudo-second-order equation. The thermodynamic parameters (ΔG, ΔH and ΔS) indicated that the adsorption of Pb(II) ions were feasible, spontaneous and endothermic at 25-80°C. XRD analysis indicated the presence of Pb(0) on the S-NaOH-NZVI surface. This study suggests that the modified sineguelas waste by NZVI particles can be prepared at low cost and the materials are environmentally benign for the removal of Pb(II) ions, and likely many other heavy metal ions, from water. Copyright © 2014 Elsevier Inc. All rights reserved.

ZIP14 and DMT1 in the liver, pancreas, and heart are differentially regulated by iron deficiency and overload: implications for tissue iron uptake in iron-related disorders

PubMed Central

Nam, Hyeyoung; Wang, Chia-Yu; Zhang, Lin; Zhang, Wei; Hojyo, Shintaro; Fukada, Toshiyuki; Knutson, Mitchell D.

2013-01-01

The liver, pancreas, and heart are particularly susceptible to iron-related disorders. These tissues take up plasma iron from transferrin or non-transferrin-bound iron, which appears during iron overload. Here, we assessed the effect of iron status on the levels of the transmembrane transporters, ZRT/IRT-like protein 14 and divalent metal-ion transporter-1, which have both been implicated in transferrin- and non-transferrin-bound iron uptake. Weanling male rats (n=6/group) were fed an iron-deficient, iron-adequate, or iron-overloaded diet for 3 weeks. ZRT/IRT-like protein 14, divalent metal-ion transporter-1 protein and mRNA levels in liver, pancreas, and heart were determined by using immunoblotting and quantitative reverse transcriptase polymerase chain reaction analysis. Confocal immunofluorescence microscopy was used to localize ZRT/IRT-like protein 14 in the liver and pancreas. ZRT/IRT-like protein 14 and divalent metal-ion transporter-1 protein levels were also determined in hypotransferrinemic mice with genetic iron overload. Hepatic ZRT/IRT-like protein 14 levels were found to be 100% higher in iron-loaded rats than in iron-adequate controls. By contrast, hepatic divalent metal-ion transporter-1 protein levels were 70% lower in iron-overloaded animals and nearly 3-fold higher in iron-deficient ones. In the pancreas, ZRT/IRT-like protein 14 levels were 50% higher in iron-overloaded rats, and in the heart, divalent metal-ion transporter-1 protein levels were 4-fold higher in iron-deficient animals. At the mRNA level, ZRT/IRT-like protein 14 expression did not vary with iron status, whereas divalent metal-ion transporter-1 expression was found to be elevated in iron-deficient livers. Immunofluorescence staining localized ZRT/IRT-like protein 14 to the basolateral membrane of hepatocytes and to acinar cells of the pancreas. Hepatic ZRT/IRT-like protein 14, but not divalent metal-ion transporter-1, protein levels were elevated in iron-loaded hypotransferrinemic

Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

DOE PAGES

Sougrati, Moulay T.; Darwiche, Ali; Liu, Xiaohiu; ...

2016-03-16

Here we report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not requiremore » heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g -1 for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M x(NCN) y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Ultimately, their electrochemical activity and performances open the way to the design of a novel family of anode materials.« less

Comprehensive Utilization of Iron and Phosphorus from High-Phosphorus Refractory Iron Ore

NASA Astrophysics Data System (ADS)

Sun, Yongsheng; Zhang, Qi; Han, Yuexin; Gao, Peng; Li, Guofeng

2018-02-01

An innovative process of coal-based reduction followed by magnetic separation and dephosphorization was developed to simultaneously recover iron and phosphorus from one typical high-phosphorus refractory iron ore. The experimental results showed that the iron minerals in iron ore were reduced to metallic iron during the coal-based reduction and the phosphorus was enriched in the metallic iron phase. The CaO-SiO2-FeO-Al2O3 slag system was used in the dephosphorization of metallic iron. A hot metal of 99.17% Fe and 0.10% P was produced with Fe recovery of 84.41%. Meanwhile, a dephosphorization slag of 5.72% P was obtained with P recovery of 67.23%. The contents of impurities in hot metal were very low, and it could be used as feedstock for steelmaking after a secondary refining. Phosphorus in the dephosphorization slag mainly existed in the form of a 5CaO·P2O5·SiO2 solid solution where the P2O5 content is 13.10%. At a slag particle size of 20.7 μm (90% passing), 94.54% of the P2O5 could be solubilized in citric acid, indicating the slag met the feedstock requirements in phosphate fertilizer production. Consequently, the proposed process achieved simultaneous Fe and P recovery, paving the way to comprehensive utilization of high-phosphorus refractory iron ore.

Metallic iron for safe drinking water provision: Considering a lost knowledge.

PubMed

Mwakabona, Hezron T; Ndé-Tchoupé, Arnaud Igor; Njau, Karoli N; Noubactep, Chicgoua; Wydra, Kerstin D

2017-06-15

Around year 1890, the technology of using metallic iron (Fe 0 ) for safe drinking water provision was already established in Europe. The science and technology to manufacture suitable Fe 0 materials were known and further developed in this period. Scientists had then developed skills to (i) explore the suitability of individual Fe 0 materials (e.g. iron filling, sponge iron) for selected applications, and (ii) establish treatment processes for households and water treatment plants. The recent (1990) discovery of Fe 0 as reactive agent for environmental remediation and water treatment has not yet considered this ancient knowledge. In the present work, some key aspects of the ancient knowledge are presented together with some contemporised interpretations, in an attempt to demonstrate the scientific truth contained therein. It appears that the ancient knowledge is an independent validation of the scientific concept that in water treatment (Fe 0 /H 2 O system) Fe 0 materials are generators of contaminant collectors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nanoscale Metal Oxide Semiconductors for Gas Sensing

NASA Technical Reports Server (NTRS)

Hunter, Gary W.; Evans, Laura; Xu, Jennifer C.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Michael J.

2011-01-01

A report describes the fabrication and testing of nanoscale metal oxide semiconductors (MOSs) for gas and chemical sensing. This document examines the relationship between processing approaches and resulting sensor behavior. This is a core question related to a range of applications of nanotechnology and a number of different synthesis methods are discussed: thermal evaporation- condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed, providing a processing overview to developers of nanotechnology- based systems. The results of a significant amount of testing and comparison are also described. A comparison is made between SnO2, ZnO, and TiO2 single-crystal nanowires and SnO2 polycrystalline nanofibers for gas sensing. The TECsynthesized single-crystal nanowires offer uniform crystal surfaces, resistance to sintering, and their synthesis may be done apart from the substrate. The TECproduced nanowire response is very low, even at the operating temperature of 200 C. In contrast, the electrospun polycrystalline nanofiber response is high, suggesting that junction potentials are superior to a continuous surface depletion layer as a transduction mechanism for chemisorption. Using a catalyst deposited upon the surface in the form of nanoparticles yields dramatic gains in sensitivity for both nanostructured, one-dimensional forms. For the nanowire materials, the response magnitude and response rate uniformly increase with increasing operating temperature. Such changes are interpreted in terms of accelerated surface diffusional processes, yielding greater access to chemisorbed oxygen species and faster dissociative chemisorption, respectively. Regardless of operating temperature, sensitivity of the nanofibers is a factor of 10 to 100 greater than that of nanowires with the same catalyst for the same test condition. In summary, nanostructure appears critical to governing the reactivity, as measured by electrical

Evaluation of the effect of divalent metal transporter 1 gene polymorphism on blood iron, lead and cadmium levels

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

Kayaaltı, Zeliha, E-mail: kayaalti@ankara.edu.tr; Akyüzlü, Dilek Kaya; Söylemezoğlu, Tülin

Divalent metal transporter 1 (DMT1), a member of the proton-coupled metal ion transporter family, mediates transport of ferrous iron from the lumen of the intestine into the enterocyte and export of iron from endocytic vesicles. It has an affinity not only for iron but also for other divalent cations including manganese, cobalt, nickel, cadmium, lead, copper, and zinc. DMT1 is encoded by the SLC11a2 gene that is located on chromosome 12q13 in humans and express four major mammalian isoforms (1A/+IRE, 1A/-IRE, 2/+IRE and 2/-IRE). Mutations or polymorphisms of DMT1 gene may have an impact on human health by disturbing metalmore » trafficking. To study the possible association of DMT1 gene with the blood levels of some divalent cations such as iron, lead and cadmium, a single nucleotide polymorphism (SNP) (IVS4+44C/A) in DMT1 gene was investigated in 486 unrelated and healthy individuals in a Turkish population by method of polymerase chain reaction–restriction fragment length polymorphism (PCR–RFLP). The genotype frequencies were found as 49.8% homozygote typical (CC), 38.3% heterozygote (CA) and 11.9% homozygote atypical (AA). Metal levels were analyzed by dual atomic absorption spectrometer system and the average levels of iron, lead and cadmium in the blood samples were 446.01±81.87 ppm, 35.59±17.72 ppb and 1.25±0.87 ppb, respectively. Individuals with the CC genotype had higher blood iron, lead and cadmium levels than those with AA and CA genotypes. Highly statistically significant associations were detected between IVS4+44 C/A polymorphism in the DMT1 gene and iron and lead levels (p=0.001 and p=0.036, respectively), but no association was found with cadmium level (p=0.344). This study suggested that DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, lead and cadmium levels. - Highlights: • DMT1 IVS4+44 C/A polymorphism is associated with inter-individual variations in blood iron, cadmium and lead levels. �

Iron-Targeting Antitumor Activity of Gallium Compounds and Novel Insights Into Triapine®-Metal Complexes

PubMed Central

Antholine, William E.

2013-01-01

Abstract Significance: Despite advances made in the treatment of cancer, a significant number of patients succumb to this disease every year. Hence, there is a great need to develop new anticancer agents. Recent Advances: Emerging data show that malignant cells have a greater requirement for iron than normal cells do and that proteins involved in iron import, export, and storage may be altered in cancer cells. Therefore, strategies to perturb these iron-dependent steps in malignant cells hold promise for the treatment of cancer. Recent studies show that gallium compounds and metal-thiosemicarbazone complexes inhibit tumor cell growth by targeting iron homeostasis, including iron-dependent ribonucleotide reductase. Chemical similarities of gallium(III) with iron(III) enable the former to mimic the latter and interpose itself in critical iron-dependent steps in cellular proliferation. Newer gallium compounds have emerged with additional mechanisms of action. In clinical trials, the first-generation-compound gallium nitrate has exhibited activity against bladder cancer and non-Hodgkin's lymphoma, while the thiosemicarbazone Triapine® has demonstrated activity against other tumors. Critical Issues: Novel gallium compounds with greater cytotoxicity and a broader spectrum of antineoplastic activity than gallium nitrate should continue to be developed. Future Directions: The antineoplastic activity and toxicity of the existing novel gallium compounds and thiosemicarbazone-metal complexes should be tested in animal tumor models and advanced to Phase I and II clinical trials. Future research should identify biologic markers that predict tumor sensitivity to gallium compounds. This will help direct gallium-based therapy to cancer patients who are most likely to benefit from it. Antioxid. Redox Signal. 00, 000–000. PMID:22900955

Direct in situ observation of metallic glass deformation by real-time nano-scale indentation

NASA Astrophysics Data System (ADS)

Gu, Lin; Xu, Limei; Zhang, Qingsheng; Pan, Deng; Chen, Na; Louzguine-Luzgin, Dmitri V.; Yao, Ke-Fu; Wang, Weihua; Ikuhara, Yuichi

2015-03-01

A common understanding of plastic deformation of metallic glasses (MGs) at room temperature is that such deformation occurs via the formation of runaway shear bands that usually lead to catastrophic failure of MGs. Here we demonstrate that inhomogeneous plastic flow at nanoscale can evolve in a well-controlled manner without further developing of shear bands. It is suggested that the sample undergoes an elasto-plastic transition in terms of quasi steady-state localized shearing. During this transition, embryonic shear localization (ESL) propagates with a very slow velocity of order of ~1 nm/s without the formation of a hot matured shear band. This finding further advances our understanding of the microscopic deformation process associated with the elasto-plastic transition and may shed light on the theoretical development of shear deformation in MGs.

Nanoscale zero-valent iron-assisted soil washing for the removal of potentially toxic elements.

PubMed

Boente, C; Sierra, C; Martínez-Blanco, D; Menéndez-Aguado, J M; Gallego, J R

2018-05-15

The present study focuses on soil washing enhancement via soil pretreatment with nanoscale zero-valent iron (nZVI) for the remediation of potentially toxic elements. To this end, soil polluted with As, Cu, Hg, Pb and Sb was partitioned into various grain sizes (500-2000, 125-500 and <125 μm). The fractions were pretreated with nZVI and subsequently subjected, according to grain size, to Wet-High Intensity Magnetic Separation (WHIMS) or hydrocycloning. The results were compared with those obtained in the absence of nanoparticles. An exhaustive characterization of the magnetic signal of the nanoparticles was done. This provided valuable information regarding potentially toxic elements (PTEs) fate, and allowed a metallurgical accounting correction considering the dilution effects caused by nanoparticle addition. As a result, remarkable recovery yields were obtained for Cu, Pb and Sb, which concentrated with the nZVI in the magnetically separated fraction (WHIMS tests) and underflow (hydrocyclone tests). In contrast, Hg, concentrated in the non-magnetic fraction and overflow respectively, while the behavior of As was unaltered by the nZVI pretreatment. All things considered, the addition of nZVI enhanced the efficiency of soil washing, particularly for larger fractions (125-2000 μm). The proposed methodology lays the foundations for nanoparticle utilization in soil washing operations. Copyright © 2018 Elsevier B.V. All rights reserved.

Plastic deformation and failure mechanisms in nano-scale notched metallic glass specimens under tensile loading

NASA Astrophysics Data System (ADS)

Dutta, Tanmay; Chauniyal, Ashish; Singh, I.; Narasimhan, R.; Thamburaja, P.; Ramamurty, U.

2018-02-01

In this work, numerical simulations using molecular dynamics and non-local plasticity based finite element analysis are carried out on tensile loading of nano-scale double edge notched metallic glass specimens. The effect of acuteness of notches as well as the metallic glass chemical composition or internal material length scale on the plastic deformation response of the specimens are studied. Both MD and FE simulations, in spite of the fundamental differences in their nature, indicate near-identical deformation features. Results show two distinct transitions in the notch tip deformation behavior as the acuity is increased, first from single shear band dominant plastic flow localization to ligament necking, and then to double shear banding in notches that are very sharp. Specimens with moderately blunt notches and composition showing wider shear bands or higher material length scale characterizing the interaction stress associated with flow defects display profuse plastic deformation and failure by ligament necking. These results are rationalized from the role of the interaction stress and development of the notch root plastic zones.

Evaluation on the Nanoscale Zero Valent Iron Based Microbial Denitrification for Nitrate Removal from Groundwater

NASA Astrophysics Data System (ADS)

Peng, Lai; Liu, Yiwen; Gao, Shu-Hong; Chen, Xueming; Xin, Pei; Dai, Xiaohu; Ni, Bing-Jie

2015-07-01

Nanoscale zero valent iron (NZVI) based microbial denitrification has been demonstrated to be a promising technology for nitrate removal from groundwater. In this work, a mathematical model is developed to evaluate the performance of this new technology and to provide insights into the chemical and microbial interactions in the system in terms of nitrate reduction, ammonium accumulation and hydrogen turnover. The developed model integrates NZVI-based abiotic reduction of nitrate, NZVI corrosion for hydrogen production and hydrogen-based microbial denitrification and satisfactorily describes all of the nitrate and ammonium dynamics from two systems with highly different conditions. The high NZVI corrosion rate revealed by the model indicates the high reaction rate of NZVI with water due to their large specific surface area and high surface reactivity, leading to an effective microbial nitrate reduction by utilizing the produced hydrogen. The simulation results further suggest a NZVI dosing strategy (3-6 mmol/L in temperature range of 30-40 °C, 6-10 mmol/L in temperature range of 15-30 °C and 10-14 mmol/L in temperature range of 5-15 °C) during groundwater remediation to make sure a low ammonium yield and a high nitrogen removal efficiency.

Evaluation on the Nanoscale Zero Valent Iron Based Microbial Denitrification for Nitrate Removal from Groundwater

PubMed Central

Peng, Lai; Liu, Yiwen; Gao, Shu-Hong; Chen, Xueming; Xin, Pei; Dai, Xiaohu; Ni, Bing-Jie

2015-01-01

Nanoscale zero valent iron (NZVI) based microbial denitrification has been demonstrated to be a promising technology for nitrate removal from groundwater. In this work, a mathematical model is developed to evaluate the performance of this new technology and to provide insights into the chemical and microbial interactions in the system in terms of nitrate reduction, ammonium accumulation and hydrogen turnover. The developed model integrates NZVI-based abiotic reduction of nitrate, NZVI corrosion for hydrogen production and hydrogen-based microbial denitrification and satisfactorily describes all of the nitrate and ammonium dynamics from two systems with highly different conditions. The high NZVI corrosion rate revealed by the model indicates the high reaction rate of NZVI with water due to their large specific surface area and high surface reactivity, leading to an effective microbial nitrate reduction by utilizing the produced hydrogen. The simulation results further suggest a NZVI dosing strategy (3–6 mmol/L in temperature range of 30–40 °C, 6–10 mmol/L in temperature range of 15–30 °C and 10–14 mmol/L in temperature range of 5–15 °C) during groundwater remediation to make sure a low ammonium yield and a high nitrogen removal efficiency. PMID:26199053

Binding of heavy metal ions in aggregates of microbial cells, EPS and biogenic iron minerals measured in-situ using metal- and glycoconjugates-specific fluorophores

NASA Astrophysics Data System (ADS)

Hao, Likai; Guo, Yuan; Byrne, James M.; Zeitvogel, Fabian; Schmid, Gregor; Ingino, Pablo; Li, Jianli; Neu, Thomas R.; Swanner, Elizabeth D.; Kappler, Andreas; Obst, Martin

2016-05-01

Aggregates consisting of bacterial cells, extracellular polymeric substances (EPS) and Fe(III) minerals formed by Fe(II)-oxidizing bacteria are common at bulk or microscale chemical interfaces where Fe cycling occurs. The high sorption capacity and binding capacity of cells, EPS, and minerals controls the mobility and fate of heavy metals. However, it remains unclear to which of these component(s) the metals will bind in complex aggregates. To clarify this question, the present study focuses on 3D mapping of heavy metals sorbed to cells, glycoconjugates that comprise the majority of EPS constituents, and Fe(III) mineral aggregates formed by the phototrophic Fe(II)-oxidizing bacteria Rhodobacter ferrooxidans SW2 using confocal laser scanning microscopy (CLSM) in combination with metal- and glycoconjugates-specific fluorophores. The present study evaluated the influence of glycoconjugates, microbial cell surfaces, and (biogenic) Fe(III) minerals, and the availability of ferrous and ferric iron on heavy metal sorption. Analyses in this study provide detailed knowledge on the spatial distribution of metal ions in the aggregates at the sub-μm scale, which is essential to understand the underlying mechanisms of microbe-mineral-metal interactions. The heavy metals (Au3+, Cd2+, Cr3+, CrO42-, Cu2+, Hg2+, Ni2+, Pd2+, tributyltin (TBT) and Zn2+) were found mainly sorbed to cell surfaces, present within the glycoconjugates matrix, and bound to the mineral surfaces, but not incorporated into the biogenic Fe(III) minerals. Statistical analysis revealed that all ten heavy metals tested showed relatively similar sorption behavior that was affected by the presence of sorbed ferrous and ferric iron. Results in this study showed that in addition to the mineral surfaces, both bacterial cell surfaces and the glycoconjugates provided most of sorption sites for heavy metals. Simultaneously, ferrous and ferric iron ions competed with the heavy metals for sorption sites on the organic

Removal of Arsenic (III, V) from aqueous solution by nanoscale zero-valent iron stabilized with starch and carboxymethyl cellulose

PubMed Central

2014-01-01

In this work, synthetic nanoscale zerovalent iron (NZVI) stabilized with two polymers, Starch and Carboxymethyl cellulose (CMC) were examined and compared for their ability in removing As (III) and As (V) from aqueous solutions as the most promising iron nanoparticles form for arsenic removal. Batch operations were conducted with different process parameters such as contact time, nanoparticles concentration, initial arsenic concentration and pH. Results revealed that starch stabilized particles (S-nZVI) presented an outstanding ability to remove both arsenate and arsenite and displayed ~ 36.5% greater removal for As (V) and 30% for As (III) in comparison with CMC-stabilized nanoparticles (C-nZVI). However, from the particle stabilization viewpoint, there is a clear trade off to choosing the best stabilized nanoparticles form. Removal efficiency was enhanced with increasing the contact time and iron loading but reduced with increasing initial As (III, V) concentrations and pH. Almost complete removal of arsenic (up to 500 μg/L) was achieved in just 5 min when the S-nZVI mass concentration was 0.3 g/L and initial solution pH of 7 ± 0.1. The maximum removal efficiency of both arsenic species was obtained at pH = 5 ± 0.1 and starched nanoparticles was effective in slightly acidic and natural pH values. The adsorption kinetics fitted well with pseudo-second-order model and the adsorption data obeyed the Langmuir equation with a maximum adsorption capacity of 14 mg/g for arsenic (V), and 12.2 mg/g for arsenic (III). It could be concluded that starch stabilized Fe0 nanoparticles showed remarkable potential for As (III, V) removal from aqueous solution e.g. contaminated water. PMID:24860660

System and method for producing metallic iron

DOEpatents

Bleifuss, Rodney L; Englund, David J; Iwasaki, Iwao; Fosnacht, Donald R; Brandon, Mark M; True, Bradford G

2013-09-17

A hearth furnace for producing metallic iron material has a furnace housing having a drying/preheat zone, a conversion zone, a fusion zone, and optionally a cooling zone, the conversion zone is between the drying/preheat zone and the fusion zone. A moving hearth is positioned within the furnace housing. A hood or separation barrier within at least a portion of the conversion zone, fusion zone or both separates the fusion zone into an upper region and a lower region with the lower region adjacent the hearth and the upper region adjacent the lower region and spaced from the hearth. An injector introduces a gaseous reductant into the lower region adjacent the hearth. A combustion region may be formed above the hood or separation barrier.

Iron Isotope Systematics

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

Dauphas, Nicolas; John, Seth G.; Rouxel, Olivier

Iron is a ubiquitous element with a rich (i.e., complex) chemical behavior. It possesses three oxidation states, metallic iron (Fe0), ferrous iron (Fe2+) and ferric iron (Fe3+). The distribution of these oxidation states is markedly stratified in the Earth.

Nano-metal Oxides: Exposure and Engineering Control Assessment

PubMed Central

Garcia, Alberto; Sparks, Christopher; Martinez, Kenneth; Topmiller, Jennifer L.; Eastlake, Adrienne; Geraci, Charles L.

2017-01-01

This paper discusses the evaluation of a facility that produces high quality engineered nanomaterials. These ENMs consist of various metals including iron, nickel, silver, manganese, and palladium. Although occupational exposure levels are not available for these metals, studies have indicated that it may be prudent to keep exposures to the nano-scale metal as low as possible. Previous In vitro studies indicated that in comparison with a material’s larger (parent) counterpart, nanomaterials can move easily through cell membranes and can cause severe toxic effects on human health. The in vitro studies showed that the toxicological effects specific to exposure to nanoscale nickel oxide and nickel have been found to be more inflammatory and toxic than larger-sized nickel particles and can decrease cell metabolic activity, arrest the G2-M cell cycle, and increase cell death. An in vitro study on exposure to iron nanoparticles indicated that the reactive oxygen species produced by exposure may increase cell permeability thereby increasing the potential for vascular movement. Much of the data available on palladium focus on dermal or ingestion exposure; the chronic effects are not well understood. Given the available limited data on the metals evaluated, caution is warranted. One should always keep in mind that the current OELs were not developed specifically for nanoscale particles. With limited data suggesting that certain nanoparticles may be more toxic than the larger counterparts of the same material; employers should attempt to control emissions of these particles at the source, to limit the potential for exposure. Evidence suggests that in general some nanomaterials can be more toxic than their macro-scale counterparts, and therefore caution is warranted. It appears that the personal protective equipment utilized by the employee was appropriate for this type of operation. It should be noted that the use of respiratory protection should not be used as sole

Metallation and mismetallation of iron and manganese proteins in vitro and in vivo: the class I ribonucleotide reductases as a case study.

PubMed

Cotruvo, Joseph A; Stubbe, Joanne

2012-10-01

How cells ensure correct metallation of a given protein and whether a degree of promiscuity in metal binding has evolved are largely unanswered questions. In a classic case, iron- and manganese-dependent superoxide dismutases (SODs) catalyze the disproportionation of superoxide using highly similar protein scaffolds and nearly identical active sites. However, most of these enzymes are active with only one metal, although both metals can bind in vitro and in vivo. Iron(ii) and manganese(ii) bind weakly to most proteins and possess similar coordination preferences. Their distinct redox properties suggest that they are unlikely to be interchangeable in biological systems except when they function in Lewis acid catalytic roles, yet recent work suggests this is not always the case. This review summarizes the diversity of ways in which iron and manganese are substituted in similar or identical protein frameworks. As models, we discuss (1) enzymes, such as epimerases, thought to use Fe(II) as a Lewis acid under normal growth conditions but which switch to Mn(II) under oxidative stress; (2) extradiol dioxygenases, which have been found to use both Fe(II) and Mn(II), the redox role of which in catalysis remains to be elucidated; (3) SODs, which use redox chemistry and are generally metal-specific; and (4) the class I ribonucleotide reductases (RNRs), which have evolved unique biosynthetic pathways to control metallation. The primary focus is the class Ib RNRs, which can catalyze formation of a stable radical on a tyrosine residue in their β2 subunits using either a di-iron or a recently characterized dimanganese cofactor. The physiological roles of enzymes that can switch between iron and manganese cofactors are discussed, as are insights obtained from the studies of many groups regarding iron and manganese homeostasis and the divergent and convergent strategies organisms use for control of protein metallation. We propose that, in many of the systems discussed

35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

35. GREY IRON TUMBLERS, IN THE GREY IRON FOUNDRY ROTATE CASTINGS WITH SHOT TO REMOVE AND SURFACE OXIDES AND REMAINING EXCESS METALS. - Stockham Pipe & Fittings Company, Grey Iron Foundry, 4000 Tenth Avenue North, Birmingham, Jefferson County, AL

75 FR 81212 - Floor-Standing Metal-Top Ironing Tables and Certain Parts Thereof from the People's Republic of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-27

... Ironing Tables and Certain Parts Thereof from the People's Republic of China: Extension of Time Limit for... parts thereof from the People's Republic of China. See Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of China: Preliminary Results of Antidumping Duty...

77 FR 1455 - Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-10

... Ironing Tables and Certain Parts Thereof From the People's Republic of China: Extension of Time Limit for... parts thereof from the People's Republic of China. See Floor-Standing, Metal-Top Ironing Tables and Certain Parts Thereof From the People's Republic of China: Preliminary Results of Antidumping Duty...

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes.

PubMed

Li, Lili; Chen, Can; Chen, Long; Zhu, Zixue; Hu, Jianli

2014-03-18

This study explores catalytic decomposition of phosphine (PH3) using iron group metals (Co, Ni) and metal oxides (Fe2O3, Co(3)O4, NiO) supported on carbon nanotubes (CNTs). The catalysts are synthesized by means of a deposition-precipitation method. The morphology, structure, and composition of the catalysts are characterized using a number of analytical instrumentations, including high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, BET surface area measurement, and inductively coupled plasma. The activity of the catalysts in the PH3 decomposition reaction is measured and correlated with their surface and structural properties. The characterization results show that phosphidation occurs on the catalyst surface, and the resulting metal phosphides act as an active phase in the PH3 decomposition reaction. Cobalt phosphide, CoP, is formed on Co/CNTs and Co(3)O4/CNTs, whereas iron phosphide, FeP, is formed on Fe2O3/CNTs. In contrast, phosphorus-rich phosphide NiP2 is formed on Ni/CNTs and NiO/CNTs. The initial activities of the catalysts are shown in the following sequence: Ni/CNTs > Co/CNTs > Co(3)O4/CNTs >NiO/CNTs > Fe2O3/CNTs, whereas activities of metal phosphides are shown in the following order: CoP > NiP2 > FeP. The catalytic activity of metal phosphides is attributed to their electronic properties. Cobalt phosphide formed on Co/CNTs and Co(3)O4/CNTs exhibits not only the highest activity, but also long-term stability in the PH3 decomposition reaction.

Micro-Intertexture Carbon-Free Iron Sulfides as Advanced High Tap Density Anodes for Rechargeable Batteries.

PubMed

Xiao, Ying; Hwang, Jang-Yeon; Sun, Yang-Kook

2017-11-15

Numerous materials have been considered as promising electrode materials for rechargeable batteries; however, developing efficient materials to achieving good cycling performance and high volumetric energy capacity simultaneously remains a great challenge. Considering the appealing properties of iron sulfides, which include low cost, high theoretical capacity, and favorable electrochemical conversion mechanism, in this work, we demonstrate the feasibility of carbon-free microscale Fe 1-x S as high-efficiency anode materials for rechargeable batteries by designing hierarchical intertexture architecture. The as-prepared intertexture Fe 1-x S microspheres constructed from nanoscale units take advantage of both the long cycle life of nanoscale units and the high tap density (1.13 g cm -3 ) of the micro-intertexture Fe 1-x S. As a result, high capacities of 1089.2 mA h g -1 (1230.8 mA h cm -3 ) and 624.7 mA h g -1 (705.9 mA h cm -3 ) were obtained after 100 cycles at 1 A g -1 in Li-ion and Na-ion batteries, respectively, demonstrating one of the best performances for iron sulfide-based electrodes. Even after deep cycling at 20 A g -1 , satisfactory capacities could be retained. Related results promote the practical application of metal sulfides as high-capacity electrodes with high rate capability for next-generation rechargeable batteries.

Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity.

PubMed

Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David

2011-10-10

A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal transports and enrichments in iron depositions hosted in basaltic rocks. II: Metal rich fluids and Fe origin

NASA Astrophysics Data System (ADS)

Zhang, Ronghua; Zhang, Xuetong; Hu, Shumin

2015-12-01

This study focuses on revealing the mechanism of metal transport, enrichment and Fe origin of iron deposition during water basalt interactions occurred in basaltic rocks. Observations of the iron deposits (anhydrite-magnetite-pyroxene type deposits) hosted in K-rich basaltic rocks in the Mesozoic volcanic area of the Middle-Lower Yangtze River valley, China, indicate that the mechanism of metal transport and enrichment for those deposits are significant objective to scientists, and the Fe origin problem is not well resolved. Here the metal transport, enrichment and iron origin have been investigated in high temperature experiments of water basaltic interactions. These deposits were accompanying a wide zone with metal alteration. The effects of hydrothermal alteration on major rock-forming element concentrations in basaltic rock were investigated by systematically comparing the chemical compositions of altered rocks with those of fresh rocks. In the deposits, these metals are distributed throughout altered rocks that exhibit vertical zoning from the deeper to the shallow. Then, combined with the investigations of the metal-alterations, we performed kinetic experiments of water-basaltic rock interactions using flow-through reactors in open systems at temperatures from 20 °C to 550 °C, 23-34 MPa. Release rates for the rock-forming elements from the rocks have been measured. Experiments provide the release rates for various elements at a large temperature range, and indicate that the dissolution rates (release rates) for various elements vary with temperature. Si, Al, and K have high release rates at temperatures from 300 °C to 500 °C; the maximum release rates (RMX) for Si are reached at temperatures from 300 °C to 400 °C. The RMXs for Ca, Mg, and Fe are at low temperatures from 20 °C to 300 °C. Results demonstrate that Fe is not released from 400 °C to 550 °C, and indicate that when deep circling fluids passed through basaltic rocks, Fe was not mobile, and

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Metal mobilization by iron- and sulfur-oxidizing bacteria in a multiple extreme mine tailings in the Atacama Desert, Chile.

PubMed

Korehi, H; Blöthe, M; Sitnikova, M A; Dold, B; Schippers, A

2013-03-05

The marine shore sulfidic mine tailings dump at the Chañaral Bay in the Atacama Desert, northern Chile, is characterized by extreme acidity, high salinity, and high heavy metals concentrations. Due to pyrite oxidation, metals (especially copper) are mobilized under acidic conditions and transported toward the tailings surface and precipitate as secondary minerals (Dold, Environ. Sci. Technol. 2006, 40, 752-758.). Depth profiles of total cell counts in this almost organic-carbon free multiple extreme environment showed variable numbers with up to 10(8) cells g(-1) dry weight for 50 samples at four sites. Real-time PCR quantification and bacterial 16S rRNA gene diversity analysis via clone libraries revealed a dominance of Bacteria over Archaea and the frequent occurrence of the acidophilic iron(II)- and sulfur-oxidizing and iron(III)-reducing genera Acidithiobacillus, Alicyclobacillus, and Sulfobacillus. Acidophilic chemolithoautotrophic iron(II)-oxidizing bacteria were also frequently found via most-probable-number (MPN) cultivation. Halotolerant iron(II)-oxidizers in enrichment cultures were active at NaCl concentrations up to 1 M. Maximal microcalorimetrically determined pyrite oxidation rates coincided with maxima of the pyrite content, total cell counts, and MPN of iron(II)-oxidizers. These findings indicate that microbial pyrite oxidation and metal mobilization preferentially occur in distinct tailings layers at high salinity. Microorganisms for biomining with seawater salt concentrations obviously exist in nature.

Emerging ferroelectric transistors with nanoscale channel materials: the possibilities, the limitations

NASA Astrophysics Data System (ADS)

Hong, Xia

2016-03-01

Combining the nonvolatile, locally switchable polarization field of a ferroelectric thin film with a nanoscale electronic material in a field effect transistor structure offers the opportunity to examine and control a rich variety of mesoscopic phenomena and interface coupling. It is also possible to introduce new phases and functionalities into these hybrid systems through rational design. This paper reviews two rapidly progressing branches in the field of ferroelectric transistors, which employ two distinct classes of nanoscale electronic materials as the conducting channel, the two-dimensional (2D) electron gas graphene and the strongly correlated transition metal oxide thin films. The topics covered include the basic device physics, novel phenomena emerging in the hybrid systems, critical mechanisms that control the magnitude and stability of the field effect modulation and the mobility of the channel material, potential device applications, and the performance limitations of these devices due to the complex interface interactions and challenges in achieving controlled materials properties. Possible future directions for this field are also outlined, including local ferroelectric gate control via nanoscale domain patterning and incorporating other emergent materials in this device concept, such as the simple binary ferroelectrics, layered 2D transition metal dichalcogenides, and the 4d and 5d heavy metal compounds with strong spin-orbit coupling.

Heavy Metals Induce Iron Deficiency Responses at Different Hierarchic and Regulatory Levels1[OPEN

PubMed Central

2017-01-01

In plants, the excess of several heavy metals mimics iron (Fe) deficiency-induced chlorosis, indicating a disturbance in Fe homeostasis. To examine the level at which heavy metals interfere with Fe deficiency responses, we carried out an in-depth characterization of Fe-related physiological, regulatory, and morphological responses in Arabidopsis (Arabidopsis thaliana) exposed to heavy metals. Enhanced zinc (Zn) uptake closely mimicked Fe deficiency by leading to low chlorophyll but high ferric-chelate reductase activity and coumarin release. These responses were not caused by Zn-inhibited Fe uptake via IRON-REGULATED TRANSPORTER (IRT1). Instead, Zn simulated the transcriptional response of typical Fe-regulated genes, indicating that Zn affects Fe homeostasis at the level of Fe sensing. Excess supplies of cobalt and nickel altered root traits in a different way from Fe deficiency, inducing only transient Fe deficiency responses, which were characterized by a lack of induction of the ethylene pathway. Cadmium showed a rather inconsistent influence on Fe deficiency responses at multiple levels. By contrast, manganese evoked weak Fe deficiency responses in wild-type plants but strongly exacerbated chlorosis in irt1 plants, indicating that manganese antagonized Fe mainly at the level of transport. These results show that the investigated heavy metals modulate Fe deficiency responses at different hierarchic and regulatory levels and that the interaction of metals with physiological and morphological Fe deficiency responses is uncoupled. Thus, this study not only emphasizes the importance of assessing heavy metal toxicities at multiple levels but also provides a new perspective on how Fe deficiency contributes to the toxic action of individual heavy metals. PMID:28500270

Phytotoxicity and uptake of nanoscale zero-valent iron (nZVI) by two plant species.

PubMed

Ma, Xingmao; Gurung, Arun; Deng, Yang

2013-01-15

Use of nano-scale zero valent iron (nZVI) for the treatment of various environmental pollutants has been proven successful. However, large scale introduction of engineered nanomaterials such as nZVI into the environment has recently attracted serious concerns. There is an urgent need to investigate the environmental fate and impact of nZVI due to the scope of its application. The goal of this study was to evaluate the toxicity and accumulation of bare nZVI by two commonly encountered plant species: cattail (Typha latifolia) and hybrid poplars (Populous deltoids×Populous nigra). Plant seedlings were grown hydroponically in a greenhouse and dosed with different concentrations of nZVI (0-1000 mg/L) for four weeks. The nZVI exhibited strong toxic effect on Typha at higher concentrations (>200 mg/L) but enhanced plant growth at lower concentrations. nZVI also significantly reduced the transpiration and growth of hybrid poplars at higher concentrations. Microscopic images indicated that large amount of nZVI coated on plant root surface as irregular aggregates and some nZVI penetrated into several layers of epidermal cells. Transmission electron microscope (TEM) and scanning transmission electron microscope (STEM) confirmed the internalization of nZVI by poplar root cells but similar internalization was not observed for Typha root cells. The upward transport to shoots was minimal for both plant species. Copyright © 2012 Elsevier B.V. All rights reserved.

Iron and iron-related proteins in asbestosis.

EPA Science Inventory

ABSTRACT: We tested the postulate that iron homeostasis is altered among patients diagnosed to have asbestosis. Lung tissue from six individuals diagnosed to have had asbestosis at autopsy was stained for iron, ferritin, divalent metal transporter 1 (DMT1), and ferroportin 1 (FP...

Localized temperature and chemical reaction control in nanoscale space by nanowire array.

PubMed

Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

2011-11-09

We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time < 2 μs). By taking advantage of this capability, several nanoscale chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.

Magnetization and Magnetoresistance in Iron Intercalated Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Choe, Jesse

The understanding of magnetism in strongly correlated electronic systems is a vital area of research. Not only is it linked to other phenomena like high temperature superconductivity in the cuprates and iron pnictides, but magnetic materials have been used in electronics since before the computer. As it becomes harder to prop up Moore's law by increasing the density of transistors, mankind must look towards new methods to improve technology or risk stagnation. Research into alternative materials for technology, such as transition metal dichalcogenides, is a promising direction of research to maintain the rate of technological improvement. Our work focuses on the effect of iron intercalation in TiS2. Single crystals of FexTiS 2 (0 ≤ x ≤ 1) were grown using vapor transport. Anisotropic susceptibility and magnetization measurements of the samples were measured, showing ferromagnetism and sharp switching behavior in the magnetization. Finally electrical transport measurements were taken, both with and without field. Measurements of magnetoresistance for x = 0.2 and 0.3 show large magnetoresistance (up to ˜ 60%) and an atypical 'bowtie' shape.

Zero-valent iron particles embedded on the mesoporous silica-carbon for chromium (VI) removal from aqueous solution

NASA Astrophysics Data System (ADS)

Xiong, Kun; Gao, Yuan; Zhou, Lin; Zhang, Xianming

2016-09-01

Nanoscale zero-valent iron (nZVI) particles were embedded on the walls of mesoporous silica-carbon (MSC) under the conditions of high-temperature carbonization and reduction and used to remove chromium (VI) from aqueous solution. The structure and textural properties of nZVI-MSC were characterized by the powder X-ray diffraction, transmission electron microscopy and N2 adsorption and desorption. The results show that nZVI-MSC has highly ordered mesoporous structure and large surface area, indistinguishable with that of MSC. Compared with the support MSC and iron particles supported on the activated carbon (nZVI/AC), nZVI-MSC exhibited much higher Cr(VI) removal efficiency with about 98 %. The removal process obeys a pseudo first-order model. Such excellent performance of nZVI-MSC could be ascribed to the large surface and iron particles embedded on the walls of the MSC, forming an intimate contact with the MSC. It is proposed that this feature might create certain micro-electrode on the interface of iron particles and MSC, which prevented the formation of metal oxide on the surface and provided fresh Fe surface for Cr(VI) removal.

Synthesis of kaolin supported nanoscale zero-valent iron and its degradation mechanism of Direct Fast Black G in aqueous solution

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

Jin, Xiaoying; Chen, Zhengxian; Zhou, Rongbing

2015-01-15

Graphical abstract: UV–visible spectra of DFBG solution using K-nZVI (1:1) nanoparticles. (a) Before reaction; (b) during reaction; (c) after reaction. - Highlights: • Kaolin-supported Fe{sup 0} nanoparticle (K-nZVI) was synthesized. • Degradation of Direct Fast Black by K-nZVI was studied. • K-nZVI was characterized by SEM, XRD, UV and FIIR. • Degradation mechanism of Direct Fast Black was proposed. - Abstract: Calcinated kaolin supported nanoscale zero-valent iron (K-nZVI) was synthesized and used for the removal of tetrad azo-group dye-Direct Fast Black G (DFBG) from aqueous solution. The results demonstrated that after reacting for 10 min with an initial concentration ofmore » DFBG 100 mg L{sup −1} (pH 9.49), 78.60% of DFBG was removed using K-nZVI, while only 41.39% and 12.56% of DFBG were removed using nZVI and kaolin, respectively. K-nZVI with a mass ratio of nZVI nanoparticles versus kaolin at 1:1 was found to have a high degree of reactivity. Furthermore, scanning electron microscopy (SEM) confirmed that nZVI was better dispersed when kaolin was present. XRD patterns indicated that iron oxides were formed after reaction. Fourier transforms infrared spectra (FTIR) and UV–visible demonstrated that the peak in the visible light region of DFBG was degraded and new bands were observed. Kinetics studies showed that the degradation of DFBG fitted well to the pseudo first-order model. The degradation of DFBG by K-nZVI was based on its adsorption onto kaolin and iron oxides, and subsequently reduction using nZVI was proposed. A significant outcome emerged in that 99.84% of DFBG in wastewater was removed using K-nZVI after reacting for 60 min.« less

New understanding of nano-scale interstitial dislocation loops in BCC iron

NASA Astrophysics Data System (ADS)

Gao, N.; Chen, J.; Kurtz, R. J.; Wang, Z. G.; Zhang, R. F.; Gao, F.

2017-11-01

Complex states of nanoscale interstitial dislocation loop can be described by its habit plane and Burgers vector. Using atomistic simulations, we provide direct evidences on the change of the habit plane of a 1/2〈1 1 1〉 loop from {1 1 1} to {1 1 0} and {2 1 1}, in agreement with TEM observations. A new {1 0 0} habit plane of this loop is also predicted by simulations. The non-conservation of the Burgers vector is approved theoretically for: (1) dislocation reactions between loops with different Burgers vectors and (2) the transition between 〈1 0 0〉 loops and 1/2〈1 1 1〉 loops. The rotation from a 1/2〈1 1 1〉 to a 〈1 0 0〉 loop has also been explored, which occurs at 570 K for time on the order of 10 s. The dislocation-precipitate phase duality and change of habit plane are then proposed as new features for nano-scale dislocation loops.

Synthesis Functional and Constructional Nanomaterials on a Basis Carbide Tungsten, Molybdenum and Metals of a Triad of Iron in Ionic Melts

NASA Astrophysics Data System (ADS)

Kushkhov, H. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

2011-04-01

Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

Magnetic mapping of iron in rodent spleen

PubMed Central

Blissett, Angela R.; Ollander, Brooke; Penn, Brittany; McTigue, Dana M.; Agarwal, Gunjan

2016-01-01

Evaluation of iron distribution and density in biological tissues is important to understand the pathogenesis of a variety of diseases and the fate of exogenously administered iron-based carriers and contrast agents. Iron distribution in tissues is typically characterized via histochemical (Perl’s) stains or immunohistochemistry for ferritin, the major iron storage protein. A more accurate mapping of iron can be achieved via ultrastructural transmission electron microscopy (TEM) based techniques, which involve stringent sample preparation conditions. In this study, we elucidate the capability of magnetic force microscopy (MFM) as a label-free technique to map iron at the nanoscale level in rodent spleen tissue. We complemented and compared our MFM results with those obtained using Perl’s staining and TEM. Our results show how MFM mapping corresponded to sizes of iron-rich lysosomes at a resolution comparable to that of TEM. In addition MFM is compatible with tissue sections commonly prepared for routine histology. PMID:27890658

Method for producing iron-based catalysts

DOEpatents

Farcasiu, Malvina; Kaufman, Phillip B.; Diehl, J. Rodney; Kathrein, Hendrik

1999-01-01

A method for preparing an acid catalyst having a long shelf-life is provided comprising doping crystalline iron oxides with lattice-compatible metals and heating the now-doped oxide with halogen compounds at elevated temperatures. The invention also provides for a catalyst comprising an iron oxide particle having a predetermined lattice structure, one or more metal dopants for said iron oxide, said dopants having an ionic radius compatible with said lattice structure; and a halogen bound with the iron and the metal dopants on the surface of the particle.

Nanoscale RRAM-based synaptic electronics: toward a neuromorphic computing device.

PubMed

Park, Sangsu; Noh, Jinwoo; Choo, Myung-Lae; Sheri, Ahmad Muqeem; Chang, Man; Kim, Young-Bae; Kim, Chang Jung; Jeon, Moongu; Lee, Byung-Geun; Lee, Byoung Hun; Hwang, Hyunsang

2013-09-27

Efforts to develop scalable learning algorithms for implementation of networks of spiking neurons in silicon have been hindered by the considerable footprints of learning circuits, which grow as the number of synapses increases. Recent developments in nanotechnologies provide an extremely compact device with low-power consumption.In particular, nanoscale resistive switching devices (resistive random-access memory (RRAM)) are regarded as a promising solution for implementation of biological synapses due to their nanoscale dimensions, capacity to store multiple bits and the low energy required to operate distinct states. In this paper, we report the fabrication, modeling and implementation of nanoscale RRAM with multi-level storage capability for an electronic synapse device. In addition, we first experimentally demonstrate the learning capabilities and predictable performance by a neuromorphic circuit composed of a nanoscale 1 kbit RRAM cross-point array of synapses and complementary metal-oxide-semiconductor neuron circuits. These developments open up possibilities for the development of ubiquitous ultra-dense, ultra-low-power cognitive computers.

Modified composites based on mesostructured iron oxyhydroxide and synthetic minerals: a potential material for the treatment of various toxic heavy metals and its toxicity.

PubMed

Chung, Seung-Gun; Ryu, Jae-Chun; Song, Mi-Kyung; An, Byungryul; Kim, Song-Bae; Lee, Sang-Hyup; Choi, Jae-Woo

2014-02-28

The composites of mesostructured iron oxyhydroxide and/or commercial synthetic zeolite were investigated for use in the removal of toxic heavy metals, such as cadmium, copper, lead and arsenic, from aqueous solution. Four types of adsorbents, dried alginate beads (DABs), synthetic-zeolite impregnated beads (SZIBs), meso-iron-oxyhydroxide impregnated beads (MIOIBs) and synthetic-zeolite/meso-iron-oxyhydroxide composite beads (SZMIOIBs), were prepared for heavy metal adsorption tests. Laboratory experiments were conducted to investigate the removal efficiencies of cations and anions of heavy metals and the possibility of regenerating the adsorbents. Among these adsorbents, the MIOIBs can simultaneously remove cations and anions of heavy metals; they have high adsorption capacities for lead (60.1mgg(-1)) and arsenic (71.9mgg(-1)) compared with other adsorbents, such as DABs (158.1 and 0.0mgg(-1)), SZIB (42.9 and 0.0mgg(-1)) and SZMIOIB (54.0 and 5.9mgg(-1)) for lead and arsenic, respectively. Additionally, the removal efficiency was consistent at approximately 90%, notwithstanding repetitive regeneration. The characteristics of meso-iron-oxyhydroxide powder were confirmed by X-ray diffraction, Brunauer-Emmett-Teller and transmission electron microscopy. We also performed a comparative toxicity study that indicated that much lower concentrations of the powdered form of mesostructured iron oxyhydroxide had stronger cytotoxicity than the granular form. These results suggest that the granular form of meso iron oxyhydroxide is a more useful and safer adsorbent for heavy metal treatment than the powdered form. This research provides promising results for the application of MIOIBs as an adsorbent for various heavy metals from wastewater and sewage. Copyright © 2013 Elsevier B.V. All rights reserved.

Application of nanoscale zero-valent iron tracer to delineate groundwater flow paths between a screened well and an open well in fractured rock

NASA Astrophysics Data System (ADS)

Chuang, P. Y.; Chiu, Y.; Liou, Y. H.; Teng, M. H.; Chia, Y.

2016-12-01

Fracture flow is of importance for water resources as well as the investigation of contaminant pathways. In this study, a novel characterization approach of nanoscale zero-valent iron (nZVI) tracer test was developed to accurately identify the connecting fracture zones of preferential flow between a screened well and an open well. Iron nanoparticles are magnetic and can be attracted by a magnet. This feature make it possible to design a magnet array for attracting nZVI particles at the tracer inlet to characterize the location of incoming tracer in the observation well. This novel approach was tested at two experiment wells with well hydraulic connectivity in a hydrogeological research station in central Taiwan. A heat-pulse flowmeter can be used to detect changes in flow velocity for delineating permeable fracture zones in the borehole and providing the design basis for the tracer test. Then, the most permeable zone in the injection well was hydraulically isolated by well screen to prevent the injected nZVI particles from being stagnated at the hole bottom. Afterwards, another hydraulic test was implemented to re-examine the hydraulic connectivity between the two wells. When nZVI slurry was injected in the injection well, they migrated through connected permeable fractures to the observation well. A breakthrough curve, observed by the fluid conductivity sensor in the observation well, indicated the arrival of nZVI slurry. The iron nanoparticles attracted to the magnets in the observation well provide the position of tracer inlet, which corroborates well with the depth of a permeable zone delineated by the flowmeter. This article demonstrates the potential of nano-iron tracer test to provide the quantitative information of fracture flow paths in fractured rock.

Highly repeatable nanoscale phase coexistence in vanadium dioxide films

NASA Astrophysics Data System (ADS)

Huffman, T. J.; Lahneman, D. J.; Wang, S. L.; Slusar, T.; Kim, Bong-Jun; Kim, Hyun-Tak; Qazilbash, M. M.

2018-02-01

It is generally believed that in first-order phase transitions in materials with imperfections, the formation of phase domains must be affected to some extent by stochastic (probabilistic) processes. The stochasticity would lead to unreliable performance in nanoscale devices that have the potential to exploit the transformation of physical properties in a phase transition. Here we show that stochasticity at nanometer length scales is completely suppressed in the thermally driven metal-insulator transition (MIT) in sputtered vanadium dioxide (V O2 ) films. The nucleation and growth of domain patterns of metallic and insulating phases occur in a strikingly reproducible way. The completely deterministic nature of domain formation and growth in films with imperfections is a fundamental and unexpected finding about the kinetics of this material. Moreover, it opens the door for realizing reliable nanoscale devices based on the MIT in V O2 and similar phase-change materials.

System and method for producing metallic iron

DOEpatents

Bleifuss, Rodney L [Grand Rapids, MN; Englund, David J [Bovey, MN; Iwasaki, Iwao [Grand Rapids, MN; Fosnacht, Donald R [Hermantown, MN; Brandon, Mark M [Charlotte, NC; True, Bradford G [Charlotte, NC

2012-01-17

A hearth furnace 10 for producing metallic iron material has a furnace housing 11 having a drying/preheat zone 12, a conversion zone 13, a fusion zone 14, and optionally a cooling zone 15, the conversion zone 13 is between the drying/preheat zone 12 and the fusion zone 14. A moving hearth 20 is positioned within the furnace housing 11. A hood or separation barrier 30 within at least a portion of the conversion zone 13, fusion zone 14 or both separates the fusion zone 14 into an upper region and a lower region with the lower region adjacent the hearth 20 and the upper region adjacent the lower region and spaced from the hearth 20. An injector introduces a gaseous reductant into the lower region adjacent the hearth 20. A combustion region may be formed above the hood or separation barrier.

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

PubMed

Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

2014-07-01

Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

Nanoscale control of an interfacial metal-insulator transition at room temperature.

PubMed

Cen, C; Thiel, S; Hammerl, G; Schneider, C W; Andersen, K E; Hellberg, C S; Mannhart, J; Levy, J

2008-04-01

Experimental and theoretical investigations have demonstrated that a quasi-two-dimensional electron gas (q-2DEG) can form at the interface between two insulators: non-polar SrTiO3 and polar LaTiO3 (ref. 2), LaAlO3 (refs 3-5), KTaO3 (ref. 7) or LaVO3 (ref. 6). Electronically, the situation is analogous to the q-2DEGs formed in semiconductor heterostructures by modulation doping. LaAlO3/SrTiO3 heterostructures have recently been shown to exhibit a hysteretic electric-field-induced metal-insulator quantum phase transition for LaAlO3 thicknesses of 3 unit cells. Here, we report the creation and erasure of nanoscale conducting regions at the interface between two insulating oxides, LaAlO3 and SrTiO3. Using voltages applied by a conducting atomic force microscope (AFM) probe, the buried LaAlO3/SrTiO3 interface is locally and reversibly switched between insulating and conducting states. Persistent field effects are observed using the AFM probe as a gate. Patterning of conducting lines with widths of approximately 3 nm, as well as arrays of conducting islands with densities >10(14) inch(-2), is demonstrated. The patterned structures are stable for >24 h at room temperature.

A novel approach for rapidly and cost-effectively assessing toxicity of toxic metals in acidic water using an acidophilic iron-oxidizing biosensor.

PubMed

Yang, Shih-Hung; Cheng, Kuo-Chih; Liao, Vivian Hsiu-Chuan

2017-11-01

Contamination by heavy metals and metalloids is a serious environmental and health concern. Acidic wastewaters are often associated with toxic metals which may enter and spread into agricultural soils. Several biological assays have been developed to detect toxic metals; however, most of them can only detect toxic metals in a neutral pH, not in an acidic environment. In this study, an acidophilic iron-oxidizing bacterium (IOB) Strain Y10 was isolated, characterized, and used to detect toxic metals toxicity in acidic water at pH 2.5. The colorimetric acidophilic IOB biosensor was based on the inhibition of the iron oxidizing ability of Strain Y10, an acidophilic iron-oxidizing bacterium, by metals toxicity. Our results showed that Strain Y10 is acidophilic iron-oxidizing bacterium. Thiobacillus caldus medium (TCM) (pH 2.5) supplied with both S 4 O 6 2- and glucose was the optimum growth medium for Strain Y10. The optimum temperature and pH for the growth of Strain Y10 was 45 °C and pH 2.5, respectively. Our study demonstrates that the color-based acidophilic IOB biosensor can be semi-quantitatively observed by eye or quantitatively measured by spectrometer to detect toxicity from multiple toxic metals at pH 2.5 within 45 min. Our study shows that monitoring toxic metals in acidic water is possible by using the acidophilic IOB biosensor. Our study thus provides a novel approach for rapid and cost-effective detection of toxic metals in acidic conditions that can otherwise compromise current methods of chemical analysis. This method also allows for increased efficiency when screening large numbers of environmental samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Production of iron from metallurgical waste

DOEpatents

Hendrickson, David W; Iwasaki, Iwao

2013-09-17

A method of recovering metallic iron from iron-bearing metallurgical waste in steelmaking comprising steps of providing an iron-bearing metallurgical waste containing more than 55% by weight FeO and FeO equivalent and a particle size of at least 80% less than 10 mesh, mixing the iron-bearing metallurgical waste with a carbonaceous material to form a reducible mixture where the carbonaceous material is between 80 and 110% of the stoichiometric amount needed to reduce the iron-bearing waste to metallic iron, and as needed additions to provide a silica content between 0.8 and 8% by weight and a ratio of CaO/SiO.sub.2 between 1.4 and 1.8, forming agglomerates of the reducible mixture over a hearth material layer to protect the hearth, heating the agglomerates to a higher temperature above the melting point of iron to form nodules of metallic iron and slag material from the agglomerates by melting.

The role of iron in cancer.

PubMed

Weinberg, E D

1996-02-01

Numerous laboratory and clinical investigations over the past few decades have observed that one of the dangers of iron is its ability to favour neoplastic cell growth. The metal is carcinogenic due to its catalytic effect on the formation of hydroxyl radicals, suppression of the activity of host defence cells and promotion of cancer cell multiplication. In both animals and humans, primary neoplasms develop at body sites of excessive iron deposits. The invaded host attempts to withhold iron from the cancer cells via sequestration of the metal in newly formed ferritin. The host also endeavours to withdraw the metal from cancer cells via macrophage synthesis of nitric oxide. Quantitative evaluation of body iron and of iron-withholding proteins has prognostic value in cancer patients. Procedures associated with lowering host iron intake and inducing host cell iron efflux can assist in prevention and management of neoplastic diseases. Pharmaceutical methods for depriving neoplastic cells of iron are being developed in experimental and clinical protocols.

Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

PubMed

Tejirian, Ani; Xu, Feng

2010-12-01

Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

Sulfur-Mediated Electron Shuttling Sustains Microbial Long-Distance Extracellular Electron Transfer with the Aid of Metallic Iron Sulfides.

PubMed

Kondo, Katsuhito; Okamoto, Akihiro; Hashimoto, Kazuhito; Nakamura, Ryuhei

2015-07-07

In addition to serving as an energy source for microbial growth, iron sulfides are proposed to act as naturally occurring electrical wires that mediate long-distance extracellular electron transfer (EET) and bridge spatially discrete redox environments. These hypothetical EET reactions stand on the abilities of microbes to use the interfacial electrochemistry of metallic/semiconductive iron sulfides to maintain metabolisms; however, the mechanisms of these phenomena remain unexplored. To obtain insight into EET to iron sulfides, we monitored EET at the interface between Shewanella oneidensis MR-1 cells and biomineralized iron sulfides in an electrochemical cell. Respiratory current steeply increased with the concomitant formation of poorly crystalline mackinawite (FeS) minerals, indicating that S. oneidensis has the ability to exploit extracellularly formed metallic FeS for long-distance EET. Deletion of major proteins of the metal-reduction (Mtr) pathway (OmcA, MtrC, CymA, and PilD) caused only subtle effects on the EET efficiency, a finding that sharply contrasts the majority of studies that report that the Mtr pathway is indispensable for the reduction of metal oxides and electrodes. The gene expression analyses of polysulfide and thiosulfate reductase suggest the existence of a sulfur-mediated electron-shuttling mechanism by which HS(-) ions and water-soluble polysulfides (HS(n)(-), where n ≥ 2) generated in the periplasmic space deliver electrons from cellular metabolic processes to cell surface-associated FeS. The finding of this Mtr-independent pathway indicates that polysulfide reductases complement the function of outer-membrane cytochromes in EET reactions and, thus, significantly expand the number of microbial species potentially capable of long-distance EET in sulfur-rich anoxic environments.

MASS TRANSPORT EFFECTS ON THE KINETICS OF NITROBENZENE REDUCTION BY IRON METAL. (R827117)

EPA Science Inventory

To evaluate the importance of external mass transport on the overall rates of
contaminant reduction by iron metal (Fe⁰), we have compared measured
rates of surface reaction for nitrobenzene (ArNO₂) to estimated rates
of external mass transport...

Iron Homeostasis in Mycobacterium tuberculosis: Mechanistic Insights into Siderophore-Mediated Iron Uptake

PubMed Central

2016-01-01

Mycobacterium tuberculosis requires iron for normal growth but faces a limitation of the metal ion due to its low solubility at biological pH and the withholding of iron by the mammalian host. The pathogen expresses the Fe3+-specific siderophores mycobactin and carboxymycobactin to chelate the metal ion from insoluble iron and the host proteins transferrin, lactoferrin, and ferritin. Siderophore-mediated iron uptake is essential for the survival of M. tuberculosis, as knockout mutants, which were defective in siderophore synthesis or uptake, failed to survive in low-iron medium and inside macrophages. But as excess iron is toxic due to its catalytic role in the generation of free radicals, regulation of iron uptake is necessary to maintain optimal levels of intracellular iron. The focus of this review is to present a comprehensive overview of iron homeostasis in M. tuberculosis that is discussed in the context of mycobactin biosynthesis, transport of iron across the mycobacterial cell envelope, and storage of excess iron. The clinical significance of the serum iron status and the expression of the iron-regulated protein HupB in tuberculosis (TB) patients is presented here, highlighting the potential of HupB as a marker, notably in extrapulmonary TB cases. PMID:27402628

Metallic nanoparticles and their medicinal potential. Part II: aluminosilicates, nanobiomagnets, quantum dots and cochleates.

PubMed

Loomba, Leena; Scarabelli, Tiziano

2013-09-01

Metallic miniaturization techniques have taken metals to nanoscale size where they can display fascinating properties and their potential applications in medicine. In recent years, metal nanoparticles such as aluminium, silicon, iron, cadmium, selenium, indium and calcium, which find their presence in aluminosilicates, nanobiomagnets, quantum dots (Q-dots) and cochleates, have caught attention of medical industries. The increasing impact of metallic nanoparticles in life sciences has significantly advanced the production techniques for these nanoparticles. In this Review, the various methods for the synthesis of nanoparticles are outlined, followed by their physicochemical properties, some recent applications in wound healing, diagnostic imaging, biosensing, assay labeling, antimicrobial activity, cancer therapy and drug delivery are listed, and finally their toxicological impacts are revised. The first half of this article describes the medicinal uses of two noble nanoparticles - gold and silver. This Review provides further information on the ability of aluminum, silicon, iron, selenium, indium, calcium and zinc to be used as nanoparticles in biomedical sciences. Aluminosilicates find their utility in wound healing and antibacterial growth. Iron-oxide nanoparticles enhance the properties of MRI contrast agents and are also used as biomagnets. Cadmium, selenium, tellurium and indium form the core nanostructures of tiny Q-dots used in cellular assay labeling, high-resolution cell imaging and biosensing. Cochleates have the bivalent nano ions calcium, magnesium or zinc imbedded in their structures and are considered to be highly effective agents for drug and gene delivery. The aluminosilicates, nanobiomagnets, Q-dots and cochleates are discussed in the light of their properties, synthesis and utility.

A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

2007-09-01

Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

Treatment of heavy metals by iron oxide coated and natural gravel media in Sustainable urban Drainage Systems.

PubMed

Norris, M J; Pulford, I D; Haynes, H; Dorea, C C; Phoenix, V R

2013-01-01

Sustainable urban Drainage Systems (SuDS) filter drains are simple, low-cost systems utilized as a first defence to treat road runoff by employing biogeochemical processes to reduce pollutants. However, the mechanisms involved in pollution attenuation are poorly understood. This work aims to develop a better understanding of these mechanisms to facilitate improved SuDS design. Since heavy metals are a large fraction of pollution in road runoff, this study aimed to enhance heavy metal removal of filter drain gravel with an iron oxide mineral amendment to increase surface area for heavy metal scavenging. Experiments showed that amendment-coated and uncoated (control) gravel removed similar quantities of heavy metals. Moreover, when normalized to surface area, iron oxide coated gravels (IOCGs) showed poorer metal removal capacities than uncoated gravel. Inspection of the uncoated microgabbro gravel indicated that clay particulates on the surface (a natural product of weathering of this material) augmented heavy metal removal, generating metal sequestration capacities that were competitive compared with IOCGs. Furthermore, when the weathered surface was scrubbed and removed, metal removal capacities were reduced by 20%. When compared with other lithologies, adsorption of heavy metals by microgabbro was 10-70% higher, indicating that both the lithology of the gravel, and the presence of a weathered surface, considerably influence its ability to immobilize heavy metals. These results contradict previous assumptions which suggest that gravel lithology is not a significant factor in SuDS design. Based upon these results, weathered microgabbro is suggested to be an ideal lithology for use in SuDS.

Polarization of IRON-REGULATED TRANSPORTER 1 (IRT1) to the plant-soil interface plays crucial role in metal homeostasis.

PubMed

Barberon, Marie; Dubeaux, Guillaume; Kolb, Cornelia; Isono, Erika; Zelazny, Enric; Vert, Grégory

2014-06-03

In plants, the controlled absorption of soil nutrients by root epidermal cells is critical for growth and development. IRON-REGULATED TRANSPORTER 1 (IRT1) is the main root transporter taking up iron from the soil and is also the main entry route in plants for potentially toxic metals such as manganese, zinc, cobalt, and cadmium. Previous work demonstrated that the IRT1 protein localizes to early endosomes/trans-Golgi network (EE/TGN) and is constitutively endocytosed through a monoubiquitin- and clathrin-dependent mechanism. Here, we show that the availability of secondary non-iron metal substrates of IRT1 (Zn, Mn, and Co) controls the localization of IRT1 between the outer polar domain of the plasma membrane and EE/TGN in root epidermal cells. We also identify FYVE1, a phosphatidylinositol-3-phosphate-binding protein recruited to late endosomes, as an important regulator of IRT1-dependent metal transport and metal homeostasis in plants. FYVE1 controls IRT1 recycling to the plasma membrane and impacts the polar delivery of this transporter to the outer plasma membrane domain. This work establishes a functional link between the dynamics and the lateral polarity of IRT1 and the transport of its substrates, and identifies a molecular mechanism driving polar localization of a cell surface protein in plants.

Biochar Supported Nanoscale Iron Particles for the Efficient Removal of Methyl Orange Dye in Aqueous Solutions

PubMed Central

Zhao, Shichen; Yan, Jingchun; Qian, Linbo; Chen, Mengfang

2015-01-01

The presence of organic contaminants in industrial effluents is an environmental concern of increasing global importance. One innovative technology for treating contaminated industrial effluents is nanoscale zero-valent iron supported on biochar (nZVI/BC). Based on Transmission Electron Microscopy, X-Ray Diffraction, and Brunauer-Emmett-Teller characterizations, the nZVI was well dispersed on the biochar and aggregation was dramatically reduced. Methyl orange (MO) served as the representative organic contaminant for verifying the effectiveness of the composite. Using decolorization efficiency as an indicator of treatment effectiveness, increasing doses of nZVI/BC yielded progressively better results with 98.51% of MO decolorized by 0.6 g/L of composite at an nZVI/BC mass ratio of 1:5. The superior decolorization efficiency of the nZVI/BC was attributed to the increase in the dispersion and reactivity of nZVI while biochar increasing the contact area with contaminant and the adsorption of composites. Additionally, the buffering function of acid-washed biochar could be in favor of maintaining the reactivity of nZVI. Furthermore, the aging nZVI/BC for 30 day was able to maintain the removal efficiency indicating that the oxidation of nZVI may be delayed in the presence of biochar. Therefore, the composite of nZVI/BC could represent an effective functional material for treating wastewater containing organic dyes in the future. PMID:26204523

Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks

PubMed Central

Jones, J. Graham; Warner, C. G.

1972-01-01

Graham Jones, J., and Warner, C. G. (1972).Brit. J. industr. Med.,29, 169-177. Chronic exposure to iron oxide, chromium oxide, and nickel oxide fumes of metal dressers in a steelworks. Occupational and medical histories, smoking habits, respiratory symptoms, chest radiographs, and ventilatory capacities were studied in 14 steelworkers employed as deseamers of steel ingots for periods of up to 16 years. The men were exposed for approximately five hours of each working shift to fume concentrations ranging from 1·3 to 294·1 mg/m3 made up mainly of iron oxide with varying proportions of chromium oxide and nickel oxide. Four of the men, with 14 to 16 years' exposure, showed radiological evidence of pneumoconiosis classified as ILO categories 2 or 3. Of these, two had pulmonary function within the normal range and two had measurable loss of function, moderate in one case and mild in the other. Many observers would diagnose these cases as siderosis but the authors consider that this term should be reserved for cases exposed to pure iron compounds. The correct diagnosis is mixed-dust pneumoconiosis and the loss of pulmonary function is caused by the effects of the mixture of metallic oxides. It is probable that inhalation of pure iron oxide does not cause fibrotic pulmonary changes, whereas the inhalation of iron oxide plus certain other substances obviously does. Images PMID:5021996

Metals removal from aqueous solution by iron-based bonding agents.

PubMed

Deliyanni, Eleni A; Lazaridis, Nikolaos K; Peleka, Efrosini N; Matis, Konstantinos A

2004-01-01

GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity.

PubMed

Schneider, J J; Czap, N; Hagen, J; Engstler, J; Ensling, J; Gütlich, P; Reinoehl, U; Bertagnolli, H; Luis, F; de Jongh, L J; Wark, M; Grubert, G; Hornyak, G L; Zanoni, R

2000-12-01

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active

Engineering Platinum Alloy Electrocatalysts in Nanoscale for PEMFC Application

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

He, Ting

2016-03-01

Fuel cells are expected to be a key next-generation energy source used for vehicles and homes, offering high energy conversion efficiency and minimal pollutant emissions. However, due to large overpotentials on anode and cathode, the efficiency is still much lower than theoretically predicted. During the past decades, considerable efforts have been made to investigate synergy effect of platinum alloyed with base metals. But, engineering the alloy particles in nanoscale has been a challenge. Most important challenges in developing nanostructured materials are the abilities to control size, monodispersity, microcomposition, and even morphology or self-assembly capability, so called Nanomaterials-by-Design, which requires interdisciplinarymore » collaborations among computational modeling, chemical synthesis, nanoscale characterization as well as manufacturing processing. Electrocatalysts, particularly fuel cell catalysts, are dramatically different from heterogeneous catalysts because the surface area in micropores cannot be electrochemically controlled on the same time scale as more transport accessible surfaces. Therefore, electrocatalytic architectures need minimal microporous surface area while maximizing surfaces accessible through mesopores or macropores, and to "pin" the most active, highest performance physicochemical state of the materials even when exposed to thermodynamic forces, which would otherwise drive restructuring, crystallization, or densification of the nanoscale materials. In this presentation, results of engineering nanoscale platinum alloy particles down to 2 ~ 4 nm will be discussed. Based on nature of alloyed base metals, various synthesis technologies have been studied and developed to achieve capabilities of controlling particle size and particle microcomposition, namely, core-shell synthesis, microemulsion technique, thermal decomposition process, surface organometallic chemical method, etc. The results show that by careful engineering

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles.

Use of Electrophoresis for Transporting Nano-Iron in Porous Media

EPA Science Inventory

Research was conducted to evaluate if electrophoresis could transport surface stabilized nanoscale zero-valent iron (nZVI) through fine grained sand with the intent of remediating a contaminant in situ. The experimental procedure involved determining the transport rates of poly...

Functional kaolin supported nanoscale zero-valent iron as a Fenton-like catalyst for the degradation of Direct Black G.

PubMed

Lin, Jiajiang; Sun, Mengqiang; Liu, Xinwen; Chen, Zuliang

2017-10-01

Kaolin supported nanoscale zero-valent iron (K-nZVI) is synthesized and applied as the Fenton-like oxidation catalyst to degrade a model azo dye, Direct Black G (DBG). The characterization of K-nZVI by the high resolution transmission electronmicroscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Energy Diffraction Spectrum (EDS) and X-ray diffraction (XRD) show that kaolin as a support material not only reduces the aggregation of zero-valent iron (nZVI) but also facilitates the Fenton-like oxidation by increasing the local concentration of DBG in the vicinity of nZVI. Pseudo first-order and pseudo second-order kinetic models are employed to reveal the adsorption and degradation of the DBG using K-nZVI as the catalyst. A better fit with pseudo second-order model for the adsorption process and equal excellent fits with pseudo first-order and pseudo second-order models for the degradation process are observed; the adsorption process is found to be the rate limiting step for overall reactions. The adsorption, evaluated by isotherms and thermodynamic parameters is a spontaneous and endothermic process. High-performance liquid chromatography-mass spectrometry (LC-MS) analysis was used to test degraded products in the degradation of DGB by K-nZVI. A removal mechanism based on the adsorption and degradation is proposed, including (i) prompt adsorption of DBG onto the K-nZVI surface, and (ii) oxidation of DBG by hydroxyl radicals at the K-nZVI surface. The application of K-nZVI to treat real wastewater containing azo dyes shows excellent degradation efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metabolic crossroads of iron and copper

PubMed Central

Collins, James F; Prohaska, Joseph R; Knutson, Mitchell D

2013-01-01

Interactions between the essential dietary metals, iron and copper, have been known for many years. This review highlights recent advances in iron-copper interactions with a focus on tissues and cell types important for regulating whole-body iron and copper homeostasis. Cells that mediate dietary assimilation (enterocytes) and storage and distribution (hepatocytes) of iron and copper are considered, along with the principal users (erythroid cells) and recyclers of red cell iron (reticuloendothelial macrophages). Interactions between iron and copper in the brain are also discussed. Many unanswered questions regarding the role of these metals and their interactions in health and disease emerge from this synopsis, highlighting extensive future research opportunities. PMID:20384844

Response of Southern Ocean Phytoplankton Communities to Trace Metal (including Iron) and Light Availability

NASA Astrophysics Data System (ADS)

Fietz, S.; Roychoudhury, A. N.; Thomalla, S.; Mtshali, T. N.; Philibert, R.; Van Horsten, N.; Loock, J. C.; Cloete, R.

2016-02-01

Phytoplankton primary productivity depends on macro- and micronutrient availability and in turn plays a key role in the marine biogeochemical cycles. The role of iron in regulating phytoplankton primary production and thus biogeochemical cycles in the Southern Ocean has been widely recognized; however, it also became obvious that iron is not the sole factor limiting primary production in the Southern Ocean and that light, for instance, might aggravate or relief trace nutrient limitation. We conducted a suite of ship-board incubation experiments in austral summer 2013/14, 2014/15 and winter 2015 to shed light on the complex interplay between trace metal and light limitation. We observed a strong difference in acclimation and photophysiological response depending on the environmental conditions of the in-situ communities prior to the experiment. The differences in acclimation and photophysiological responses resulted in different growth and macronutrient uptake rates. Revisited stations did, however, not always show the same responses. At at least one station we will link the incubation experiments to the in-situ vertical profiles of trace metals, macronutrients and primary productivity.

Nanoscale relaxation oscillator

DOEpatents

Zettl, Alexander K.; Regan, Brian C.; Aloni, Shaul

2009-04-07

A nanoscale oscillation device is disclosed, wherein two nanoscale droplets are altered in size by mass transport, then contact each other and merge through surface tension. The device may also comprise a channel having an actuator responsive to mechanical oscillation caused by expansion and contraction of the droplets. It further has a structure for delivering atoms between droplets, wherein the droplets are nanoparticles. Provided are a first particle and a second particle on the channel member, both being made of a chargeable material, the second particle contacting the actuator portion; and electrodes connected to the channel member for delivering a potential gradient across the channel and traversing the first and second particles. The particles are spaced apart a specified distance so that atoms from one particle are delivered to the other particle by mass transport in response to the potential (e.g. voltage potential) and the first and second particles are liquid and touch at a predetermined point of growth, thereby causing merging of the second particle into the first particle by surface tension forces and reverse movement of the actuator. In a preferred embodiment, the channel comprises a carbon nanotube and the droplets comprise metal nanoparticles, e.g. indium, which is readily made liquid.

Transport of polymer stabilized nano-scale zero-valent iron in porous media

NASA Astrophysics Data System (ADS)

Mondal, Pulin K.; Furbacher, Paul D.; Cui, Ziteng; Krol, Magdalena M.; Sleep, Brent E.

2018-05-01

This study presents a set of laboratory-scale transport experiments and numerical simulations evaluating carboxymethyl cellulose (CMC) polymer stabilized nano-scale zero-valent iron (nZVI) transport. The experiments, performed in a glass-walled two-dimensional (2D) porous medium system, were conducted to identify the effects of water specific discharge and CMC concentration on nZVI transport and to produce data for model validation. The transport and movement of a tracer lissamine green B® (LGB) dye, CMC, and CMC-nZVI were evaluated through analysis of the breakthrough curves (BTCs) at the outlets, the time-lapsed images of the plume, and retained nZVI in the sandbox. The CMC mass recovery was > 95% when injected alone and about 65% when the CMC-nZVI mixture was used. However, the mean residence time of CMC was significantly higher than that of LGB. Of significance for field implementation, viscous fingering was observed in water displacement of previously injected CMC and CMC-nZVI. The mass recovery of nZVI was lower (< 50%) than CMC recovery due to attachment onto sand grain surfaces. Consecutive CMC-nZVI injections showed higher nZVI recovery in the second injection, a factor to be considered in field trials with successive CMC-nZVI injections. Transport of LGB, CMC, and nZVI were modeled using a flow and transport model considering LGB and CMC as solutes, and nZVI as a colloid, with variable solution viscosity due to changes in CMC concentrations. The simulation results matched the experimental observations and provided estimates of transport parameters, including attachment efficiency, that can be used to predict CMC stabilized nZVI transport in similar porous media, although the extent of viscous fingering may be underpredicted. The experimental and simulation results indicated that increasing specific discharge had a greater effect on decreasing CMC-nZVI attachment efficiency (corresponding to greater possible travel distances in the field) than increasing

Iron Containing Metal-Organic Frameworks: Structure, Synthesis, and Applications in Environmental Remediation.

PubMed

Liu, Xiaocheng; Zhou, Yaoyu; Zhang, Jiachao; Tang, Lin; Luo, Lin; Zeng, Guangming

2017-06-21

Metal-organic frameworks (MOFs) with Fe content are gradually developing into an independent branch in environmental remediation, requiring economical, effective, low-toxicity strategies to the complete procedure. In this review, recent advancements in the structure, synthesis, and environmental application focusing on the mechanism are presented. The unique structure of novel design proposed specific characteristics of different iron-containing MOFs with potential innovation. Synthesis of typical MILs, NH 2 -MILs and MILs based materials reveal the basis and defect of the current method, indicating the optimal means for the actual requirements. The adsorption of various contamination with multiple interaction as well as the catalytic degradation over radicals or electron-hole pairs are reviewed. This review implied considerable prospects of iron-containing MOFs in the field of environment and a more comprehensive cognition into the challenges and potential improvement.

Nanoscale magnetic imaging using picosecond thermal gradients

NASA Astrophysics Data System (ADS)

Fuchs, Gregory

Research and development in spintronics is challenged by the lack of table-top magnetic imaging technologies that posses the simultaneous temporal resolution and spatial resolution to characterize magnetization dynamics in emerging spintronic devices. In addition, many of the most exciting magnetic material systems for spintronics are difficult to image with any method. To address this challenge, we developed a spatiotemporal magnetic microscope based on picosecond heat pulses that stroboscopically transduces an in-plane magnetization into a voltage signal. When the magnetic device contains a magnetic metal like FeCoB or NiFe, we use the time-resolved anomalous Nernst effect. When it contains a magnetic insulator/normal metal bilayer like yttrium iron garnet/platinum, we use the combination of the time-resolved longitudinal spin Seebeck effect and the inverse spin Hall effect. We demonstrate that these imaging modalities have time resolutions in the range of 10-100 ps and sensitivities in the range of 0.1 - 0.3° /√{Hz} , which enables not only static magnetic imaging, but also phase-sensitive ferromagnetic resonance imaging. One application of this technology is for magnetic torque vector imaging, which we apply to a spin Hall device. We find an unexpected variation in the spin torque vector that suggests conventional, all-electrical FMR measurements of spin torque vectors can produce a systematic error as large as 30% when quantifying the spin Hall efficiency. Finally, I will describe how time-resolved magnetic imaging can greatly exceed the spatial resolution of optical diffraction. We demonstrate scanning a sharp gold tip to create near-field thermal transfer from a picosecond laser pulse to a magnetic sample as the basis of a nanoscale spatiotemporal microscope. We gratefully acknowledge support from the AFOSR (FA9550-14-1-0243) and the NSF through the Cornell Center for Materials Research (DMR-1120296).

Iron Carbides and Nitrides: Ancient Materials with Novel Prospects.

PubMed

Ye, Zhantong; Zhang, Peng; Lei, Xiang; Wang, Xiaobai; Zhao, Nan; Yang, Hua

2018-02-07

Iron carbides and nitrides have aroused great interest in researchers, due to their excellent magnetic properties, good machinability and the particular catalytic activity. Based on these advantages, iron carbides and nitrides can be applied in various areas such as magnetic materials, biomedical, photo- and electrocatalysis. In contrast to their simple elemental composition, the synthesis of iron carbides and nitrides still has great challenges, particularly at the nanoscale, but it is usually beneficial to improve performance in corresponding applications. In this review, we introduce the investigations about iron carbides and nitrides, concerning their structure, synthesis strategy and various applications from magnetism to the catalysis. Furthermore, the future prospects are also discussed briefly. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphization and Directional Crystallization of Metals Confined in Carbon Nanotubes Investigated by in Situ Transmission Electron Microscopy.

PubMed

Tang, Dai-Ming; Ren, Cui-Lan; Lv, Ruitao; Yu, Wan-Jing; Hou, Peng-Xiang; Wang, Ming-Sheng; Wei, Xianlong; Xu, Zhi; Kawamoto, Naoyuki; Bando, Yoshio; Mitome, Masanori; Liu, Chang; Cheng, Hui-Ming; Golberg, Dmitri

2015-08-12

The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.

Potential ecological and human health risks of heavy metals in surface soils associated with iron ore mining in Pahang, Malaysia.

PubMed

Diami, Siti Merryan; Kusin, Faradiella Mohd; Madzin, Zafira

2016-10-01

The composition of heavy metals (and metalloid) in surface soils of iron ore mine-impacted areas has been evaluated of their potential ecological and human health risks. The mining areas included seven selected locations in the vicinity of active and abandoned iron ore-mining sites in Pahang, Malaysia. Heavy metals such as Fe, Mn, Cu, Zn, Co, Pb, Cr, Ni, and Cd and metalloid As were present in the mining soils of the studied area, while Cu was found exceeding the soil guideline value at all sampling locations. However, the assessment of the potential ecological risk index (RI) indicated low ecological risk (RI between 44 and 128) with respect to Cd, Pb, Cu, As, Zn, Co, and Ni in the surface soils. Contributions of potential ecological risk [Formula: see text]by metal elements to the total potential ecological RI were evident for Cd, As, Pb, and Cu. Contribution of Cu appears to be consistently greater in the abandoned mining area compared to active iron ore-mining site. For non-carcinogenic risk, no significant potential health risk was found to both children and adults as the hazard indices (HIs) were all below than 1. The lifetime cancer risk (LCR) indicated that As has greater potential carcinogenic risk compared to other metals that may induce carcinogenic effects such as Pb, Cr, and Cd, while the LCR of As for children fell within tolerable range for regulatory purposes. Irrespective of carcinogenic or non-carcinogenic risk, greater potential health risk was found among children (by an order of magnitude higher for most metals) compared to adults. The hazard quotient (HQ) and cancer risk indicated that the pathways for the risk to occur were found to be in the order of ingestion > dermal > inhalation. Overall, findings showed that some metals and metalloid were still present at comparable concentrations even long after cessation of the iron ore-mining activities.

Long-Term Field Study of Microbial Community and Dechlorinating Activity Following Carboxymethyl Cellulose-Stabilized Nanoscale Zero-Valent Iron Injection.

PubMed

Kocur, Chris M D; Lomheim, Line; Molenda, Olivia; Weber, Kela P; Austrins, Leanne M; Sleep, Brent E; Boparai, Hardiljeet K; Edwards, Elizabeth A; O'Carroll, Denis M

2016-07-19

Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes.

On the role of weak interface in crack blunting process in nanoscale layered composites

NASA Astrophysics Data System (ADS)

Li, Yi; Zhou, Qing; Zhang, Shuang; Huang, Ping; Xu, Kewei; Wang, Fei; Lu, Tianjian

2018-03-01

Heterointerface in a nanoscale metallic layered composite could improve its crack resistance. However, the influence of metallic interface structures on crack propagation has not been well understood at atomic scale. By using the method of molecular dynamics (MD) simulation, the crack propagation behavior in Cu-Nb bilayer is compared with that in Cu-Ni bilayer. We find that the weak Cu-Nb interface plays an important role in hindering crack propagation in two ways: (i) dislocation nucleation at the interface releases stress concentration for the crack to propagate; (ii) the easily sheared weak incoherent interface blunts the crack tip. The results are helpful for understanding the interface structure dependent crack resistance of nanoscale bicrystal interfaces.

The iron-chelate transporter OsYSL9 plays a role in iron distribution in developing rice grains.

PubMed

Senoura, Takeshi; Sakashita, Emi; Kobayashi, Takanori; Takahashi, Michiko; Aung, May Sann; Masuda, Hiroshi; Nakanishi, Hiromi; Nishizawa, Naoko K

2017-11-01

Rice OsYSL9 is a novel transporter for Fe(II)-nicotianamine and Fe(III)-deoxymugineic acid that is responsible for internal iron transport, especially from endosperm to embryo in developing seeds. Metal chelators are essential for safe and efficient metal translocation in plants. Graminaceous plants utilize specific ferric iron chelators, mugineic acid family phytosiderophores, to take up sparingly soluble iron from the soil. Yellow Stripe 1-Like (YSL) family transporters are responsible for transport of metal-phytosiderophores and structurally similar metal-nicotianamine complexes. Among the rice YSL family members (OsYSL) whose functions have not yet been clarified, OsYSL9 belongs to an uncharacterized subgroup containing highly conserved homologs in graminaceous species. In the present report, we showed that OsYSL9 localizes mainly to the plasma membrane and transports both iron(II)-nicotianamine and iron(III)-deoxymugineic acid into the cell. Expression of OsYSL9 was induced in the roots but repressed in the nonjuvenile leaves in response to iron deficiency. In iron-deficient roots, OsYSL9 was induced in the vascular cylinder but not in epidermal cells. Although OsYSL9-knockdown plants did not show a growth defect under iron-sufficient conditions, these plants were more sensitive to iron deficiency in the nonjuvenile stage compared with non-transgenic plants. At the grain-filling stage, OsYSL9 expression was strongly and transiently induced in the scutellum of the embryo and in endosperm cells surrounding the embryo. The iron concentration was decreased in embryos of OsYSL9-knockdown plants but was increased in residual parts of brown seeds. These results suggested that OsYSL9 is involved in iron translocation within plant parts and particularly iron translocation from endosperm to embryo in developing seeds.

The reproductive responses of earthworms (Eisenia fetida) exposed to nanoscale zero-valent iron (nZVI) in the presence of decabromodiphenyl ether (BDE209).

PubMed

Liang, Jun; Xia, Xiaoqian; Yuan, Ling; Zhang, Wei; Lin, Kuangfei; Zhou, Bingsheng; Hu, Shuangqing

2018-06-01

Reproductive toxicity of nanoscale zero-valent iron (nZVI) along with coexisting decabromodiphenyl ether (BDE209) to earthworm Eisenia fetida (E. fetida) remains unknown. In the present study, the reproductive responses of E. fetida exposed to 100, 500 and 1000 mg kg -1 of nZVI showed a significant (P < 0.05) decline up to 35.6%, 60.0% and 93.3%, respectively, compared to the controls. Expression levels of annetocin (ANN) gene indicated a remarkable (P < 0.05) down-regulation (59.2%, 58.2% and 95.0%, correspondingly), and it was positively correlated with reproductive rates (R = 0.94). Iron contents in E. fetida were also relevant to reproductive behavior (R = 0.84) and ANN expression (R = 0.75). Additionally, seminal vesicles displayed a progressive degeneration with increasing nZVI levels. The addition of BDE209 to low level of nZVI-polluted group (100 mg kg -1 dw) barely caused clear changes on reproduction, histopathology and ANN, while the coexistence resulted in significant impacts in comparison with high level of single nZVI exposure (1000 mg kg -1 dw). These observations would provide some significant information concerning joint toxicity of the two chemicals in a soil system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tissue distribution of manganese in iron-sufficient or iron-deficient rats after stainless steel welding-fume exposure.

PubMed

Park, Jung-Duck; Kim, Ki-Young; Kim, Dong-Won; Choi, Seong-Jin; Choi, Byung-Sun; Chung, Yong Hyun; Han, Jeong Hee; Sung, Jae Hyuck; Kwon, Il Hoon; Mun, Je-Hyeok; Yu, Il Je

2007-05-01

Welders can be exposed to high levels of manganese through welding fumes. Although it has already been suggested that excessive manganese exposure causes neurotoxicity, called manganism, the pathway of manganese transport to the brain with welding-fume exposure remains unclear. Iron is an essential metal that maintains a homeostasis in the body. The divalent metal transporter 1 (DMT1) transports iron and other divalent metals, such as manganese, and the depletion of iron is known to upregulate DMT1 expression. Accordingly, this study investigated the tissue distribution of manganese in iron-sufficient and iron-deficient rats after welding-fume exposure. The feeding of an iron-deficient diet for 4 wk produced a depletion of body iron, such as decreased iron levels in the serum and tissues, and upregulated the DMT1 expression in the rat duodenum. The iron-sufficient and iron-deficient rats were then exposed to welding fumes generated from manual metal arc stainless steel at a concentration of 63.5 +/- 2.3 mg/m3 for 2 h per day over a 30-day period. Animals were sacrificed on days 1, 15, and 30. The level of body iron in the iron-deficient rats was restored to the control level after the welding-fume exposure. However, the tissue distributions of manganese after the welding-fume exposure showed similar patterns in both the iron-sufficient and iron-deficient groups. The concentration of manganese increased in the lungs and liver on days 15 and 30, and increased in the olfactory bulb on day 30. Slight and heterogeneous increases of manganese were observed in different brain regions. Consequently, these findings suggest that the presence of Fe in the inhaled welding fumes may not have a significant effect on the uptake of Mn into the brain. Thus, the condition of iron deficiency did not seem to have any apparent effect on the transport of Mn into the brain after the inhalation of welding fumes.

Atomic layer deposition: an enabling technology for the growth of functional nanoscale semiconductors

NASA Astrophysics Data System (ADS)

Biyikli, Necmi; Haider, Ali

2017-09-01

In this paper, we present the progress in the growth of nanoscale semiconductors grown via atomic layer deposition (ALD). After the adoption by semiconductor chip industry, ALD became a widespread tool to grow functional films and conformal ultra-thin coatings for various applications. Based on self-limiting and ligand-exchange-based surface reactions, ALD enabled the low-temperature growth of nanoscale dielectric, metal, and semiconductor materials. Being able to deposit wafer-scale uniform semiconductor films at relatively low-temperatures, with sub-monolayer thickness control and ultimate conformality, makes ALD attractive for semiconductor device applications. Towards this end, precursors and low-temperature growth recipes are developed to deposit crystalline thin films for compound and elemental semiconductors. Conventional thermal ALD as well as plasma-assisted and radical-enhanced techniques have been exploited to achieve device-compatible film quality. Metal-oxides, III-nitrides, sulfides, and selenides are among the most popular semiconductor material families studied via ALD technology. Besides thin films, ALD can grow nanostructured semiconductors as well using either template-assisted growth methods or bottom-up controlled nucleation mechanisms. Among the demonstrated semiconductor nanostructures are nanoparticles, nano/quantum-dots, nanowires, nanotubes, nanofibers, nanopillars, hollow and core-shell versions of the afore-mentioned nanostructures, and 2D materials including transition metal dichalcogenides and graphene. ALD-grown nanoscale semiconductor materials find applications in a vast amount of applications including functional coatings, catalysis and photocatalysis, renewable energy conversion and storage, chemical sensing, opto-electronics, and flexible electronics. In this review, we give an overview of the current state-of-the-art in ALD-based nanoscale semiconductor research including the already demonstrated and future applications.

Removal of Cr(VI) from Water Using a New Reactive Material: Magnesium Oxide Supported Nanoscale Zero-Valent Iron

PubMed Central

Siciliano, Alessio

2016-01-01

The chromium pollution of water is an important environmental and health issue. Cr(VI) removal by means of metallic iron is an attractive method. Specifically, nanoscopic zero valent iron (NZVI) shows great reactivity, however, its applicability needs to be further investigated. In the present paper, NZVI was supported on MgO grains to facilitate the treatments for remediation of chromium-contaminated waters. The performances and mechanisms of the developed composite, in the removal of hexavalent chromium, were investigated by means of batch and continuous tests. Kinetic studies, under different operating conditions, showed that reduction of Cr(VI) could be expressed by a pseudo second-order reaction kinetic. The reaction rate increased with the square of Fe(0) amount, while it was inversely proportional to the initial chromium concentration. The process performance was satisfactory also under uncontrolled pH, and a limited influence of temperature was observed. The reactive material was efficiently reusable for many cycles without any regeneration treatment. The performances in continuous tests were close to 97% for about 80 pore volume of reactive material. PMID:28773785

Removal of Cr(VI) from Water Using a New Reactive Material: Magnesium Oxide Supported Nanoscale Zero-Valent Iron.

PubMed

Siciliano, Alessio

2016-08-06

The chromium pollution of water is an important environmental and health issue. Cr(VI) removal by means of metallic iron is an attractive method. Specifically, nanoscopic zero valent iron (NZVI) shows great reactivity, however, its applicability needs to be further investigated. In the present paper, NZVI was supported on MgO grains to facilitate the treatments for remediation of chromium-contaminated waters. The performances and mechanisms of the developed composite, in the removal of hexavalent chromium, were investigated by means of batch and continuous tests. Kinetic studies, under different operating conditions, showed that reduction of Cr(VI) could be expressed by a pseudo second-order reaction kinetic. The reaction rate increased with the square of Fe(0) amount, while it was inversely proportional to the initial chromium concentration. The process performance was satisfactory also under uncontrolled pH, and a limited influence of temperature was observed. The reactive material was efficiently reusable for many cycles without any regeneration treatment. The performances in continuous tests were close to 97% for about 80 pore volume of reactive material.

Application of sequential extraction analysis to Pb(II) recovery by zerovalent iron-based particles.

PubMed

Zhu, Neng-Min; Xu, Yan-Sheng; Dai, Lichun; Zhang, Yun-Fei; Hu, Guo-Quan

2018-06-05

Zerovalent iron (ZVI) is an environmental-friendly reactive reagent for recovering heavy metals. However, the detailed recovery mechanism remains unclear due to a lack of quantitative analysis of recovery products. Herein, microscale ZVI, nanoscale ZVI and Ni/Fe nanoparticles were used to recover Pb(II) in aqueous solution and a sequential extraction procedure (SEP) was applied to determine the formed lead species quantitatively. At high initial Pb(II) concentration (500 mg L -1 ), more than 99.5% of Pb(II) was immobilized by Ni/Fe and n-ZVI, whereas m-ZVI caused inferior recovery efficiency (<25%). XRD and XPS results revealed that Pb(II) was reduced to Pb 0 prior to the formation of metal hydroxides as the external shell of ZVI. SEP results showed that the fraction bound to carbonates (PbO), fraction bound to iron oxides and exchangeable fraction were the main lead species conducted by Ni/Fe, n-ZVI and m-ZVI, respectively. Consequently, (co-)precipitation and specific adsorption dominated Pb(II) recovery by Ni/Fe and n-ZVI, whereas m-ZVI conducted Pb(II) recovery mainly via weak adsorption. The reactivity of ZVI toward Pb(II) followed the increasing order of m-ZVI < n-ZVI ≤ Ni/Fe. The detailed mechanisms of Pb(II) recovery conducted by different ZVI were proposed. Copyright © 2018 Elsevier B.V. All rights reserved.

Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.

PubMed

Chu, Qianli; Duncan, Andrew J E; Papaefstathiou, Giannis S; Hamilton, Tamara D; Atkinson, Manza B J; Mariappan, S V Santhana; MacGillivray, Leonard R

2018-04-11

Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.

Corrosion resistance of cast irons and titanium alloys as reference engineered metal barriers for use in basalt geologic storage: a literature assessment

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

Charlot, L.A.; Westerman, R.E.

A survey and assessment of the literature on the corrosion resistance of cast irons and low-alloy titanium are presented. Selected engineering properties of cast iron and titanium are briefly described; however, the corrosion resistance of cast iron and titanium in aqueous solutions or in soils and their use in a basalt repository are emphasized. In evaluating the potential use of cast iron and titanium as structural barrier materials for long-lived nuclear waste packages, it is assumed that titanium has the general corrosion resistance to be used in relatively thin cross sections whereas the cost and availability of cast iron allowsmore » its use even in very thick cross sections. Based on this assumption, the survey showed that: The uniform corrosion of low-alloy titanium in a basalt environment is expected to be extremely low. A linear extrapolation of general corrosion rates with an added corrosion allowance suggests that a 3.2- to 6.4-mm-thick wall may have a life of 1000 yr. Pitting and crevice corrosion are not likely corrosion modes in basalt ground waters. It is also unlikely that stress corrosion cracking (SCC) will occur in the commercially pure (CP) titanium alloy or in palladiumor molybdenum-alloyed titanium materials. Low-alloy cast irons may be used as barrier metals if the environment surrounding the metal keeps the alloy in the passive range. The solubility of the corrosion product and the semipermeable nature of the oxide film allow significant uniform corrosion over long time periods. A linear extrapolation of high-temperature corrosion rates on carbon steels and corrosion rates of cast irons in soils gives an estimated metal penetration of 51 to 64 mm after 1000 yr. A corrosion allowance of 3 to 5 times that suggests that an acceptable cast iron wall may be from 178 to 305 mm thick. Although they cannot be fully assessed, pitting and crevice corrosion should not affect cast iron due to the ground-water chemistry of basalt.« less

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

PubMed Central

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-01-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions. PMID:26355955

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co(2+) Solution: Interactional Performance and Mechanism.

PubMed

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-10

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co(2+) solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co(2+) reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the "structural influence" crucial for the full and dynamical understanding of nZVI reactions.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+ Solution: Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions.

Enhanced Fenton-like Degradation of Trichloroethylene by Hydrogen Peroxide Activated with Nanoscale Zero Valent Iron Loaded on Biochar

PubMed Central

Yan, Jingchun; Qian, Linbo; Gao, Weiguo; Chen, Yun; Ouyang, Da; Chen, Mengfang

2017-01-01

Composite of nanoscale Zero Valent Iron (nZVI) loaded on Biochar (BC) was prepared and characterized as hydrogen peroxide (H2O2) activator for the degradation of trichloroethylene (TCE). nZVI is homogeneously loaded on lamellarly structured BC surfaces to form nZVI/BC with specific surface area (SBET) of 184.91 m2 g−1, which can efficiently activate H2O2 to achieve TCE degradation efficiency of 98.9% with TOC removal of 78.2% within 30 min under the conditions of 0.10 mmol L−1 TCE, 1.13 g L−1 nZVI/BC and 1.50 mmol L−1 H2O2. Test results from the Electron Spin Resonance (ESR) measurement and coumarin based fluorescent probe technology indicated that ∙OH radicals were the dominant species responsible for the degradation of TCE within the nZVI/BC-H2O2 system. Activation mechanism of the redox action of Fe2+/Fe3+ generated under both aerobic and anaerobic conditions from nZVI and single electron transfer process from BC surface bound C–OH to H2O2 promoted decomposition of H2O2 into ∙OH radicals was proposed. PMID:28230207

Enhanced Fenton-like Degradation of Trichloroethylene by Hydrogen Peroxide Activated with Nanoscale Zero Valent Iron Loaded on Biochar

NASA Astrophysics Data System (ADS)

Yan, Jingchun; Qian, Linbo; Gao, Weiguo; Chen, Yun; Ouyang, Da; Chen, Mengfang

2017-02-01

Composite of nanoscale Zero Valent Iron (nZVI) loaded on Biochar (BC) was prepared and characterized as hydrogen peroxide (H2O2) activator for the degradation of trichloroethylene (TCE). nZVI is homogeneously loaded on lamellarly structured BC surfaces to form nZVI/BC with specific surface area (SBET) of 184.91 m2 g-1, which can efficiently activate H2O2 to achieve TCE degradation efficiency of 98.9% with TOC removal of 78.2% within 30 min under the conditions of 0.10 mmol L-1 TCE, 1.13 g L-1 nZVI/BC and 1.50 mmol L-1 H2O2. Test results from the Electron Spin Resonance (ESR) measurement and coumarin based fluorescent probe technology indicated that •OH radicals were the dominant species responsible for the degradation of TCE within the nZVI/BC-H2O2 system. Activation mechanism of the redox action of Fe2+/Fe3+ generated under both aerobic and anaerobic conditions from nZVI and single electron transfer process from BC surface bound C-OH to H2O2 promoted decomposition of H2O2 into •OH radicals was proposed.

Evaluation of the effects of nanoscale zero-valent iron (nZVI) dispersants on intrinsic biodegradation of trichloroethylene (TCE).

PubMed

Chang, Y C; Huang, S C; Chen, K F

2014-01-01

In this study, the biodegradability of nanoscale zero-valent iron (nZVI) dispersants and their effects on the intrinsic biodegradation of trichloroethylene (TCE) were evaluated. Results of a microcosm study show that the biodegradability of three dispersants followed the sequence of: polyvinyl alcohol-co-vinyl acetate-co-itaconic acid (PV3A) > polyoxyethylene (20) sorbitan monolaurate (Tween 20) > polyacrylic acid (PAA) under aerobic conditions, and PV3A > Tween 20 > PAA under anaerobic conditions. Natural biodegradation of TCE was observed under both aerobic and anaerobic conditions. No significant effects were observed on the intrinsic biodegradation of TCE under aerobic conditions with the presence of the dispersants. The addition of PAA seemed to have a slightly adverse impact on anaerobic TCE biodegradation. Higher accumulation of the byproducts of anaerobic TCE biodegradation was detected with the addition of PV3A and Tween 20. The diversity of the microbial community was enhanced under aerobic conditions with the presence of more biodegradable PV3A and Tween 20. The results of this study indicate that it is necessary to select an appropriate dispersant for nZVI to prevent a residual of the dispersant in the subsurface. Additionally, the effects of the dispersant on TCE biodegradation and the accumulation of TCE biodegrading byproducts should also be considered.

A 2D tank test on remediation of nitrobenzene-contaminated aquifer using in-situ reactive zone with emulsified nanoscale zero-valent iron.

PubMed

Dong, Jun; Dong, Yang; Wen, Chunyu; Gao, Song; Ren, Liming; Bao, Qiburi

2018-05-15

Nitrobenzene (NB) is one of the most challenging pollutants for groundwater remediation due to its great harm and recalcitrance. Emulsified nanoscale zero-valent iron (EZVI) is considered as a promising agent for in-situ remediation of contaminated groundwater for its high reactivity, good durability and low cost. In this paper, 2D tank experiment was conducted to evaluate the effectiveness of enhanced remediation of NB-contaminated groundwater with EZVI. 9 L of EZVI solution was injected into aquifer to establish in-situ reactive zone (IRZ) before 40 d of NB contamination. Results indicate that injection of EZVI leads to 90% reduction of total NB, which is mainly converted to aniline (AN). NB concentration decreases along the flow path in the tank. Fe 2+ is generated from Fe 0 oxidation. Significant acetate and bicarbonate are released due to emulsified oil decomposition during the whole operation time. Groundwater pH maintains in neutral value (6.6-8.2) owing to the balance between organic acids and OH - released after iron oxidation. Drastic decrease of ORP and DO indicates the transformation from oxidizing to reducing condition, leading to the reduction of oxidative species (e.g. sulfate, nitrate) in subsurface. Calculation of reducing equivalents suggests that microbial breakdown of emulsified oil provides more electrons than Fe 0 oxidation does to the system. Both biotic and abiotic processes are involved in the enhanced degradation of NB. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mapping fracture flow paths with a nanoscale zero-valent iron tracer test and a flowmeter test

NASA Astrophysics Data System (ADS)

Chuang, Po-Yu; Chia, Yeeping; Chiu, Yung-Chia; Teng, Mao-Hua; Liou, Sofia Ya Hsuan

2018-02-01

The detection of preferential flow paths and the characterization of their hydraulic properties are important for the development of hydrogeological conceptual models in fractured-rock aquifers. In this study, nanoscale zero-valent iron (nZVI) particles were used as tracers to characterize fracture connectivity between two boreholes in fractured rock. A magnet array was installed vertically in the observation well to attract arriving nZVI particles and identify the location of the incoming tracer. Heat-pulse flowmeter tests were conducted to delineate the permeable fractures in the two wells for the design of the tracer test. The nZVI slurry was released in the screened injection well. The arrival of the slurry in the observation well was detected by an increase in electrical conductivity, while the depth of the connected fracture was identified by the distribution of nZVI particles attracted to the magnet array. The position where the maximum weight of attracted nZVI particles was observed coincides with the depth of a permeable fracture zone delineated by the heat-pulse flowmeter. In addition, a saline tracer test produced comparable results with the nZVI tracer test. Numerical simulation was performed using MODFLOW with MT3DMS to estimate the hydraulic properties of the connected fracture zones between the two wells. The study results indicate that the nZVI particle could be a promising tracer for the characterization of flow paths in fractured rock.

Termination of nanoscale zero-valent iron reactivity by addition of bromate as a reducing reactivity competitor

NASA Astrophysics Data System (ADS)

Mines, Paul D.; Kaarsholm, Kamilla M. S.; Droumpali, Ariadni; Andersen, Henrik R.; Lee, Wontae; Hwang, Yuhoon

2017-09-01

Remediation of contaminated groundwater by nanoscale zero-valent iron (nZVI) is widely becoming a leading environmentally friendly solution throughout the globe. Since a wide range of various nZVI-containing materials have been developed for effective remediation, it is necessary to determine an appropriate way to terminate the reactivity of any nZVI-containing material for a practical experimental procedure. In this study, bimetallic Ni/Fe-NPs were prepared to enhance overall reduction kinetics owing to the catalytic reactivity of nickel on the surface of nZVI. We have tested several chemical strategies in order to terminate nZVI reactivity without altering the concentration of volatile compounds in the solution. The strategies include surface passivation in alkaline conditions by addition of carbonate, and consumption of nZVI by a reaction competitor. Four halogenated chemicals, trichloroethylene, 1,1,1-trichloroethane, atrazine, and 4-chlorophenol, were selected and tested as model groundwater contaminants. Addition of carbonate to passivate the nZVI surface was not effective for trichloroethylene. Nitrate and then bromate were applied to competitively consume nZVI by their faster reduction kinetics. Bromate proved to be more effective than nitrate, subsequently terminating nZVI reactivity for all four of the tested halogenated compounds. Furthermore, the suggested termination method using bromate was successfully applied to obtain trichloroethylene reduction kinetics. Herein, we report the simple and effective method to terminate the reactivity of nZVI by addition of a reducing reactivity competitor.

Iron homeostasis and its disruption in mouse lung in iron deficiency and overload.

PubMed

Giorgi, Gisela; D'Anna, María Cecilia; Roque, Marta Elena

2015-10-01

What is the central question of this study? The aim was to explore the role and hitherto unclear mechanisms of action of iron proteins in protecting the lung against the harmful effects of iron accumulation and the ability of pulmonary cells to mobilize iron in iron deficiency. What is the main finding and its importance? We show that pulmonary hepcidin appears not to modify cellular iron mobilization in the lung. We propose pathways for supplying iron to the lung in iron deficiency and for protecting the lung against iron excess in iron overload, mediated by the co-ordinated action of iron proteins, such as divalent metal transporter 1, ZRT-IRE-like-protein 14, transferrin receptor, ferritin, haemochromatosis-associated protein and ferroportin. Iron dyshomeostasis is associated with several forms of chronic lung disease, but its mechanisms of action remain to be elucidated. The aim of the present study was to determine the role of the lung in whole-animal models with iron deficiency and iron overload, studying the divalent metal transporter 1 (DMT1), ZRT-IRE-like protein 14 (ZIP14), transferrin receptor (TfR), haemochromatosis-associated protein (HFE), hepcidin, ferritin and ferroportin (FPN) expression. In each model, adult CF1 mice were divided into the following groups (six mice per group): (i) iron-overload model, iron saccharate i.p. and control group (iron adequate), 0.9% NaCl i.p.; and (ii) iron-deficiency model, induced by repeated bleeding, and control group (sham operated). Proteins were assessed by immunohistochemistry and Western blot. In control mice, DMT1 was localized in the cytoplasm of airway cells, and in iron deficiency and overload it was in the apical membrane. Divalent metal transporter 1 and TfR increased in iron deficiency, without changes in iron overload. ZRT-IRE-like protein 14 decreased in airway cells in iron deficiency and increased in iron overload. In iron deficiency, HFE and FPN were immunolocalized close to the apical membrane

Reactivity of Nanoscale Zero-Valent Iron in Unbuffered Systems: Effect of pH and Fe(II) Dissolution.

PubMed

Bae, Sungjun; Hanna, Khalil

2015-09-01

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zerovalent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH systems. The reduction rate increased exponentially with respect to the NZVI concentration, and the ratio of dissolved Fe(II)/initial NZVI was related proportionally to the initial pH values, suggesting that lower pH (6-7) with low NZVI loading may slow the 4-NP reduction through acceleration of the dissolution of NZVI particles. Additional experiments using buffered pH systems confirmed that high pH values (8-9) can preserve the NZVI particles against dissolution, thereby enhancing the reduction kinetics of 4-NP. Furthermore, reduction tests using ferrous ion in suspensions of magnetite and maghemite showed that surface-bound Fe(II) on oxide coatings can play an important role in enhancing 4-NP reduction by NZVI at pH 8. These unexpected results highlight the importance of pH and Fe(II) dissolution when NZVI technology is applied to poorly buffered systems, particularly at a low amount of NZVI (i.e., <0.075 g/L).

Nanoscale decomposition of Nb-Ru-O

NASA Astrophysics Data System (ADS)

Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

2016-11-01

A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

Revealing Nanoscale Passivation and Corrosion Mechanisms of Reactive Battery Materials in Gas Environments.

PubMed

Li, Yuzhang; Li, Yanbin; Sun, Yongming; Butz, Benjamin; Yan, Kai; Koh, Ai Leen; Zhao, Jie; Pei, Allen; Cui, Yi

2017-08-09

Lithium (Li) metal is a high-capacity anode material (3860 mAh g -1 ) that can enable high-energy batteries for electric vehicles and grid-storage applications. However, Li metal is highly reactive and repeatedly consumed when exposed to liquid electrolyte (during battery operation) or the ambient environment (throughout battery manufacturing). Studying these corrosion reactions on the nanoscale is especially difficult due to the high chemical reactivity of both Li metal and its surface corrosion films. Here, we directly generate pure Li metal inside an environmental transmission electron microscope (TEM), revealing the nanoscale passivation and corrosion process of Li metal in oxygen (O 2 ), nitrogen (N 2 ), and water vapor (H 2 O). We find that while dry O 2 and N 2 (99.9999 vol %) form uniform passivation layers on Li, trace water vapor (∼1 mol %) disrupts this passivation and forms a porous film on Li metal that allows gas to penetrate and continuously react with Li. To exploit the self-passivating behavior of Li in dry conditions, we introduce a simple dry-N 2 pretreatment of Li metal to form a protective layer of Li nitride prior to battery assembly. The fast ionic conductivity and stable interface of Li nitride results in improved battery performance with dendrite-free cycling and low voltage hysteresis. Our work reveals the detailed process of Li metal passivation/corrosion and demonstrates how this mechanistic insight can guide engineering solutions for Li metal batteries.

Assessment of heavy metal accumulation in macrophyte, agricultural soil, and crop plants adjacent to discharge zone of sponge iron factory

NASA Astrophysics Data System (ADS)

Gupta, S.; Nayek, S.; Saha, R. N.; Satpati, S.

2008-08-01

The present study deals with the characterization of effluent released from sponge iron industries and distribution of heavy metals in soil and macrophytes near to effluent discharge channel. Apart from this, accumulation of heavy metals in nearby soil and vegetation system irrigated with effluent-contaminated water is also the subject of this study. Physico-chemical analysis of effluent reveals that the concentration of total suspended solids (TSS), total hardness (TH), iron (Fe2+), and oil and grease are greater than the IS (1981) norms for discharge of water into inland water body. The soil along the sides of the effluent channel also shows higher concentration of heavy metals than the background soil. The enrichment of the heavy metals are in the order of Chromium (Cr) > Iron (Fe) > Manganese (Mn) > Zinc (Zn) > Copper (Cu) > Cadmium (Cd). Macrophytes growing along the sides of the effluent channel also show significant accumulation of heavy metals almost in the same order as accumulated in soil. Higher uptake of heavy metals by these varieties reveals that these species can be used for future phytoremediation. The effluent as well as contaminated water is extensively used for irrigation for growing vegetables like tomato ( Lycopersicon esculatum) in the surrounding areas. Heavy metal accumulation in this agricultural soil are in the sequence of Cr > Fe > Mn > Zn > Cu > Cd. More or less similar type of accumulation pattern are also found in tomato plants except Fe and Zn exceeding Cr and Mn. Transfer Factor of heavy metals from soil to tomato plants (TFS) shows average value of <1, suggesting less uptake of heavy metals from soil. Among the plant parts studied, fruit shows least accumulation. Although tomato plants show some phenotypic changes, the survival of tomato plants as well as least accumulation of metals in fruit reveals their tolerance to heavy metals. Therefore it may be suggested that this plant can be grown successfully in the heavy metal

Silicate Inclusions in IAB Irons: Correlations Between Metal Composition and Inclusion Properties, and Inferences for Their Origin

NASA Astrophysics Data System (ADS)

Benedix, G. K.; McCoy, T. J.; Keil, K.

1995-09-01

IAB irons are the largest group of iron meteorites, exhibit a large range of siderophile element concentrations in their metal, and commonly contain silicate inclusions with roughly chondritic composition. They are closely related to IIICD irons [1,2] and their inclusions resemble winonaites [3]. It has been suggested that IAB's and IIICD's formed in individual impact melt pools [4,2] on a common parent body. However, it has also been suggested that fractional crystallization [5,6] of a S-saturated core could produce the observed siderophile element trends. Metal composition is correlated with silicate inclusion mineralogy in IIICD's [1], indicating reactions between solid silicates and the metallic magma in a core. These trends observed in IIICD's differ from those in IAB's, suggesting different parent bodies. A bi-modal grouping, based primarily on mineralogy and mineral abundances, was suggested for IAB inclusions [7]. However, recent recoveries of several new silicate-bearing IAB's, along with the emergence of new ideas on their origins, prompted a comprehensive study to document more fully the range of inclusions within IAB irons, to examine possible correlations between the compositions of the metallic host and the silicate inclusions, and to elucidate the origin of IAB irons. We are studying troilite-graphite-silicate inclusions in 24 IAB irons with Ni concentrations ranging from 6.6-25.0%. These include Odessa and Copiapo types [7], newly recovered meteorites (e.g., Lueders [8]) and meteorites with extreme Ni contents (e.g., Jenny's Creek, 6.8%; San Cristobal, 25.0% [9]). The inclusions exhibit a range of textures from recrystallized to partial melts (e.g., Caddo County [10]). Rigorous classification [7] is hampered by heterogeneities between group meteorites, between different samples of distinct meteorites, and within individual inclusions. While intergroup heterogeneities make comparisons between the suite of IAB's somewhat difficult, some general trends

Investigations on mobility of carbon colloid supported nanoscale zero-valent iron (nZVI) in a column experiment and a laboratory 2D-aquifer test system.

PubMed

Busch, Jan; Meißner, Tobias; Potthoff, Annegret; Oswald, Sascha E

2014-09-01

Nanoscale zero-valent iron (nZVI) has recently gained great interest in the scientific community as in situ reagent for installation of permeable reactive barriers in aquifer systems, since nZVI is highly reactive with chlorinated compounds and may render them to harmless substances. However, nZVI has a high tendency to agglomerate and sediment; therefore it shows very limited transport ranges. One new approach to overcome the limited transport of nZVI in porous media is using a suited carrier colloid. In this study we tested mobility of a carbon colloid supported nZVI particle "Carbo-Iron Colloids" (CIC) with a mean size of 0.63 μm in a column experiment of 40 cm length and an experiment in a two-dimensional (2D) aquifer test system with dimensions of 110 × 40 × 5 cm. Results show a breakthrough maximum of 82 % of the input concentration in the column experiment and 58 % in the 2D-aquifer test system. Detected residuals in porous media suggest a strong particle deposition in the first centimeters and few depositions in the porous media in the further travel path. Overall, this suggests a high mobility in porous media which might be a significant enhancement compared to bare or polyanionic stabilized nZVI.

Mammalian iron metabolism and its control by iron regulatory proteins☆

PubMed Central

Anderson, Cole P.; Shen, Lacy; Eisenstein, Richard S.; Leibold, Elizabeth A.

2013-01-01

Cellular iron homeostasis is maintained by iron regulatory proteins 1 and 2 (IRP1 and IRP2). IRPs bind to iron-responsive elements (IREs) located in the untranslated regions of mRNAs encoding protein involved in iron uptake, storage, utilization and export. Over the past decade, significant progress has been made in understanding how IRPs are regulated by iron-dependent and iron-independent mechanisms and the pathological consequences of IRP2 deficiency in mice. The identification of novel IREs involved in diverse cellular pathways has revealed that the IRP–IRE network extends to processes other than iron homeostasis. A mechanistic understanding of IRP regulation will likely yield important insights into the basis of disorders of iron metabolism. This article is part of a Special Issue entitled: Cell Biology of Metals. PMID:22610083

Chemical classification of iron meteorites. XI. Multi-element studies of 38 new irons and the high abundance of ungrouped irons from Antarctica

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

Wasson, J.T.; Ouyang, Xinwei; Wang, Jianmin

1989-03-01

The authors report concentrations of 14 elements in the metal of 38 iron meteorites and a pallasite. The meteorites are classified based on these data and on structural observations. Three samples are paired with previously classified irons; thus, these additional 35 irons raise the number of well-classified, independent iron meteorites to 598. One Yamato iron contains 342 mg/g Ni, the second highest Ni content in an IAB iron after Oktibbeha County. Two small irons from Western Australia appear to be metal nodules from mesosiderites. Several of the new irons are from Antarctica. Of 24 independent irons from Antarctica, 8 aremore » ungrouped. The fraction, 0.333, is much higher than the fraction 0.161 among all 598 classified irons. Statistical tests show that it is highly improbably ({approximately}2.9% probability) that the Antarctic population is a random sample of the larger population. The difference is probably related to the fact that the median mass of Antarctic irons is about two orders of magnitude smaller than that of non-Antarctic irons. It is doubtful that the difference results from fragmentation patterns yielding different size distributions favoring smaller masses among ungrouped irons. More likely is the possibility that smaller meteoroids tend to sample a larger number of asteroidal source regions, perhaps because small meteoroids tend to have higher ejection velocities or because small meteoroids have random-walked a greater increment of orbital semimajor axis away from that of the parent body.« less

Surface coating with Ca(OH)2 for improvement of the transport of nanoscale zero-valent iron (nZVI) in porous media.

PubMed

Wei, Cai-jie; Li, Xiao-yan

2013-01-01

A novel thermal deposition method was developed to coat Ca(OH)2 on the surface of nanoscale zero-valent iron (nZVI). The nZVI particles with the Ca(OH)2 coating layer, nZVI/Ca(OH)2, had a clear core-shell structure based on the transmission electron microscopy observations, and the Ca(OH)2 shell was identified as an amorphous phase. The Ca(OH)2 coating shell would not only function as an effective protection layer for nZVI but also improve the mobility of nZVI in porous media for its use in environmental decontamination. A 10% Ca/Fe mass ratio was found to result in a proper thickness of the Ca(OH)2 shell on the nZVI surface. Based on the filtration tests in sand columns, the Ca(OH)2-based surface coating could greatly improve the mobility and transport of nZVI particles in porous media. In addition, batch experiments were conducted to evaluate the reactivity of Ca(OH)2-coated nZVI particles for the reduction of Cr(VI) and its removal from water.

[Enhanced remediation of 4-chloronitrobenzene contaminated groundwater with nanoscale zero-valence iron (nZVI) catalyzed hydrogen peroxide (H2O2)].

PubMed

Fu, Rong-Bing

2014-04-01

Chemical oxidation-reduction technology is an important way to quickly remedy contaminated groundwater. Nanoscale zero-valent iron (nZVI) was produced by liquid-phase reduction using FeSO4 and NaBH4, and characterized by SEM and XRD. The remediation of 4-chloronitrobezene (4-CINB) contaminated groundwater at ambient temperature and pressure was conducted with the nZVI catalytic H2O2 process, and the affecting factors and degradation mechanisms were investigated. The results indicated that under initial pH 3.0 at the temperature of 30 degrees C, after 30 mins of reaction, 4-ClNB in groundwater was completely degraded when the concentrations of nZVI and H2O2 were 268.8 mg x L(-1) and 4.90 mmol x L(-1), respectively. 4-chloronitrosobenzene, 4-chlorophenylhydroxylamine, 4-chloroazoxybenzene, 4-chloroaniline, 4-chloroazobenzene, 4-benzoquinone, acetic acid, formic acid, oxalic acid and chlorine ion were identified as the major intermediates of 4-ClNB degradation after the process. A tentative pathway for the degradation of 4-ClNB was proposed.

Synthesis, dynamics and photophysics of nanoscale systems

NASA Astrophysics Data System (ADS)

Mirkovic, Tihana

The emerging field of nanotechnology, which spans diverse areas such as nanoelectronics, medicine, chemical and pharmaceutical industries, biotechnology and computation, focuses on the development of devices whose improved performance is based on the utilization of self-assembled nanoscale components exhibiting unique properties owing to their miniaturized dimensions. The first phase in the conception of such multifunctional devices based on integrated technologies requires the study of basic principles behind the functional mechanism of nanoscale components, which could originate from individual nanoobjects or result as a collective behaviour of miniaturized unit structures. The comprehensive studies presented in this thesis encompass the mechanical, dynamical and photophysical aspects of three nanoscale systems. A newly developed europium sulfide nanocrystalline material is introduced. Advances in synthetic methods allowed for shape control of surface-functionalized EuS nanocrystals and the fabrication of multifunctional EuS-CdSe hybrid particles, whose unique structural and optical properties hold promise as useful attributes of integrated materials in developing technologies. A comprehensive study based on a new class of multifunctional nanomaterials, derived from the basic unit of barcoded metal nanorods is presented. Their chemical composition affords them the ability to undergo autonomous motion in the presence of a suitable fuel. The nature of their chemically powered self-propulsion locomotion was investigated, and plausible mechanisms for various motility modes were presented. Furthermore functionalization of striped metallic nanorods has been realized through the incorporation of chemically controlled flexible hinges displaying bendable properties. The structural aspect of the light harvesting machinery of a photosynthetic cryptophyte alga, Rhodomonas CS24, and the mobility of the antenna protein, PE545, in vivo were investigated. Information obtained

Reactions of metal ions at surfaces of hydrous iron oxide

USGS Publications Warehouse

Hem, J.D.

1977-01-01

Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review

EPA Science Inventory

Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their te...

Iron Isotope Constraints on Planetesimal Core Formation

NASA Astrophysics Data System (ADS)

Jordan, M.; Young, E. D.

2016-12-01

The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured

A hard X-ray nanoprobe beamline for nanoscale microscopy

PubMed Central

Winarski, Robert P.; Holt, Martin V.; Rose, Volker; Fuesz, Peter; Carbaugh, Dean; Benson, Christa; Shu, Deming; Kline, David; Stephenson, G. Brian; McNulty, Ian; Maser, Jörg

2012-01-01

The Hard X-ray Nanoprobe Beamline (or Nanoprobe Beamline) is an X-ray microscopy facility incorporating diffraction, fluorescence and full-field imaging capabilities designed and operated by the Center for Nanoscale Materials and the Advanced Photon Source at Sector 26 of the Advanced Photon Source at Argonne National Laboratory. This facility was constructed to probe the nanoscale structure of biological, environmental and material sciences samples. The beamline provides intense focused X-rays to the Hard X-ray Nanoprobe (or Nanoprobe) which incorporates Fresnel zone plate optics and a precision laser sensing and control system. The beamline operates over X-ray energies from 3 to 30 keV, enabling studies of most elements in the periodic table, with a particular emphasis on imaging transition metals. PMID:23093770

A hard X-ray nanoprobe beamline for nanoscale microscopy.

PubMed

Winarski, Robert P; Holt, Martin V; Rose, Volker; Fuesz, Peter; Carbaugh, Dean; Benson, Christa; Shu, Deming; Kline, David; Stephenson, G Brian; McNulty, Ian; Maser, Jörg

2012-11-01

The Hard X-ray Nanoprobe Beamline (or Nanoprobe Beamline) is an X-ray microscopy facility incorporating diffraction, fluorescence and full-field imaging capabilities designed and operated by the Center for Nanoscale Materials and the Advanced Photon Source at Sector 26 of the Advanced Photon Source at Argonne National Laboratory. This facility was constructed to probe the nanoscale structure of biological, environmental and material sciences samples. The beamline provides intense focused X-rays to the Hard X-ray Nanoprobe (or Nanoprobe) which incorporates Fresnel zone plate optics and a precision laser sensing and control system. The beamline operates over X-ray energies from 3 to 30 keV, enabling studies of most elements in the periodic table, with a particular emphasis on imaging transition metals.

A luminescent ratiometric pH sensor based on a nanoscale and biocompatible Eu/Tb-mixed MOF.

PubMed

Xia, Tifeng; Zhu, Fengliang; Jiang, Ke; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2017-06-13

The precise and real-time monitoring of localized pH changes is of great importance in many engineering and environmental fields, especially for monitoring small pH changes in biological environments and living cells. Metal-organic frameworks (MOFs) with their nanoscale processability show very promising applications in bioimaging and biomonitoring, but the fabrication of nanoscale MOFs is still a challenge. In this study, we synthesized a nanoscale mixed-lanthanide metal-organic framework by a microemulsion method. The morphology and size of the NMOF can be simply adjusted by the addition of different amounts of the CTAB surfactant. This NMOF exhibits significant pH-dependent luminescence emission, which can act as a self-referenced pH sensor based on two emissions of Tb 3+ at 545 nm and Eu 3+ at 618 nm in the pH range from 3.00 to 7.00. The MTT assay and optical microscopy assay demonstrate the low cytotoxicity and good biocompatibility of the nanosensor.

Attrition of precipitated iron Fischer-Tropsch catalysts

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

Datye, A.K.; Reardon, J.; Hanprasopwattana, A.

1996-12-31

Precipitated Iron catalysts used in slurry phase bubble column reactors are known to undergo attrition during use. The attrition reduces the lifetime of the catalyst as well as causing problems in separating the product liquids from the catalyst. In this study, the authors have investigated the underlying mechanisms that lead to attrition in precipitated iron catalysts. They have discovered that attrition takes place on two length scales. On the macro scale, attrition is caused by the break-up of the weak agglomerates that constitute this catalyst into individual crystallites. Addition of binders such as kaolin does not help significantly in strengtheningmore » the catalyst particles. In addition, there is a second process leading to nanoscale attrition that is caused by the break-up of individual iron oxide crystallites into nano particles of iron carbide as the catalyst is activated for reaction. Design of attrition resistant F-T catalysts must consider these two modes of catalyst attrition. Preliminary work in the laboratory directed at improving the attrition resistance of precipitated iron catalysts will also be described in this paper.« less

Reducing As availability in calcareous soils using nanoscale zero valent iron.

PubMed

Azari, Prisa; Bostani, Abdol Amir

2017-09-01

Different methods, including the use of nanoscale zero-valent iron (NZVI), have been used to treat arsenic (As)-contaminated environments, with much less data on the use of NZVI in arsenic-calcareous-polluted soils. Accordingly, two different experiments were conducted to investigate the effects of NZVI on the removal of As from three different calcareous-polluted soils. In the first experiment, the effects of soil type (differing in the rate of clay particles and organic carbon including S1 (8.0 and 0.05%), S2 (20 and 0.2%), and S3 (20.5 and 0.8%)) and NZVI concentration (0, 50, and 100 g kg -1 of dry soil) on the removal of As extractable with distilled water were evaluated using a factorial design with three replicates. In the second experiment, the NZVI concentrations were reduced to 0, 2.5, 5.0, and 25 g kg -1 , and the NZVI contact time (0.5, 48, 96, 192, 384, and 768 h) was also tested. The analysis of variance in both experiments indicated the significant effects (P < 0.01) of the experimental treatments on the removal of As. The concentrations of available As in S3 (42.7 mg kg -1 ), S2 (20.22 mg kg -1 ), and S1 (24.22 mg kg -1 ) after using the 50 g kg -1 NZVI treatment decreased to 0, 0, and 0.05 mg kg -1 , respectively, which was not significantly different from the 100 g kg -1 NZVI treatment. In the second experiment, using the 25 g kg -1 NZVI treatment, the concentration of available As significantly decreased in S1 from 16.48 to 0.1767 mg kg -1 , in S2 from 13.34 to 0.31 mg kg -1 , and in S3 from 33.67 to 0.84 mg kg -1 . In the three soils, with increasing NZVI concentration and contact time, the concentration of available As in the solution phase significantly decreased (P = 0.01). S3, due to a higher rate of organic matter, was less responsive to the NZVI treatments than the other soils. The effectiveness of the nanoremediation method, tested in this research work, on the stabilization of As in calcareous soils, is

The impact of defect scattering on the quasi-ballistic transport of nanoscale conductors

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

Esqueda, I. S., E-mail: isanchez@isi.edu; Fritze, M.; Cress, C. D.

2015-02-28

Using the Landauer approach for carrier transport, we analyze the impact of defects induced by ion irradiation on the transport properties of nanoscale conductors that operate in the quasi-ballistic regime. Degradation of conductance results from a reduction of carrier mean free path due to the introduction of defects in the conducting channel. We incorporate scattering mechanisms from radiation-induced defects into calculations of the transmission coefficient and present a technique for extracting modeling parameters from near-equilibrium transport measurements. These parameters are used to describe degradation in the transport properties of nanoscale devices using a formalism that is valid under quasi-ballistic operation.more » The analysis includes the effects of bandstructure and dimensionality on the impact of defect scattering and discusses transport properties of nanoscale devices from the diffusive to the ballistic limit. We compare calculations with recently published measurements of irradiated nanoscale devices such as single-walled carbon nanotubes, graphene, and deep-submicron Si metal-oxide-semiconductor field-effect transistors.« less

Metal Tolerance Protein 8 Mediates Manganese Homeostasis and Iron Reallocation during Seed Development and Germination.

PubMed

Eroglu, Seckin; Giehl, Ricardo F H; Meier, Bastian; Takahashi, Michiko; Terada, Yasuko; Ignatyev, Konstantin; Andresen, Elisa; Küpper, Hendrik; Peiter, Edgar; von Wirén, Nicolaus

2017-07-01

Metal accumulation in seeds is a prerequisite for germination and establishment of plants but also for micronutrient delivery to humans. To investigate metal transport processes and their interactions in seeds, we focused on METAL TOLERANCE PROTEIN8 (MTP8), a tonoplast transporter of the manganese (Mn) subclade of cation diffusion facilitators, which in Arabidopsis ( Arabidopsis thaliana ) is expressed in embryos of seeds. The x-ray fluorescence imaging showed that expression of MTP8 was responsible for Mn localization in subepidermal cells on the abaxial side of the cotyledons and in cortical cells of the hypocotyl. Accordingly, under low Mn availability, MTP8 increased seed stores of Mn, required for efficient seed germination. In mutant embryos lacking expression of VACUOLAR IRON TRANSPORTER1 ( VIT1 ), MTP8 built up iron (Fe) hotspots in MTP8 -expressing cells types, suggesting that MTP8 transports Fe in addition to Mn. In mtp8 vit1 double mutant seeds, Mn and Fe were distributed in all cell types of the embryo. An Fe transport function of MTP8 was confirmed by its ability to complement Fe hypersensitivity of a yeast mutant defective in vacuolar Fe transport. Imbibing mtp8-1 mutant seeds in the presence of Mn or subjecting seeds to wet-dry cycles showed that MTP8 conferred Mn tolerance. During germination, MTP8 promoted reallocation of Fe from the vasculature. These results indicate that cell type-specific accumulation of Mn and Fe in seeds depends on MTP8 and that this transporter plays an important role in the generation of seed metal stores as well as for metal homeostasis and germination efficiency under challenging environmental conditions. © 2017 American Society of Plant Biologists. All Rights Reserved.

Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

PubMed Central

2016-01-01

The current status of homogeneous iron catalysis in organic chemistry is contemplated, as are the reasons why this particular research area only recently starts challenging the enduring dominance of the late and mostly noble metals over the field. Centered in the middle of the d-block and able to support formal oxidation states ranging from −II to +VI, iron catalysts hold the promise of being able to encompass organic synthesis at large. They are expected to serve reductive as well as oxidative regimes, can emulate “noble tasks”, but are also able to adopt “early” transition metal character. Since a comprehensive coverage of this multidimensional agenda is beyond the scope of an Outlook anyway, emphasis is laid in this article on the analysis of the factors that perhaps allow one to control the multifarious chemical nature of this earth-abundant metal. The challenges are significant, not least at the analytical frontier; their mastery mandates a mindset that differs from the routines that most organic chemists interested in (noble metal) catalysis tend to cultivate. This aspect notwithstanding, it is safe to predict that homogeneous iron catalysis bears the chance to enable a responsible paradigm for chemical synthesis and a sustained catalyst economy, while potentially providing substantial economic advantages. This promise will spur the systematic and in-depth investigations that it takes to upgrade this research area to strategy-level status in organic chemistry and beyond. PMID:27981231

Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

NASA Astrophysics Data System (ADS)

Kolesnik, O. N.; Astakhova, N. V.

2018-01-01

Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.

Mean-Square Amplitudes of Vibration and Anisotropic Motion of Metal Atoms in Iron Organometallics

NASA Astrophysics Data System (ADS)

Herber, Rolfe H.; Nowik, Israel

2002-12-01

Mössbauer recoil-free fraction (f) data for ferrocene [(η5-(C5H5)2Fe] over the temperature range 90≤T≤370 K have been used to calculate the mean-square-amplitude-of-vibration (msav) of the iron atom, and these data have been compared to the thermal factors (U ij ) extracted from X-ray diffraction data reported in the literature. The agreement between these two independent data sets is taken as a validation of the interpretation of the Mössbauer data in terms of the mean-square-amplitude-of-vibration of the metal atom in iron organometallic solids. The contribution of three low-frequency IR active modes of ferrocene (ω11, ω21, and ω22) to the f(T) parameter is discussed in detail.

Ferritin iron minerals are chelator targets, antioxidants, and coated, dietary iron.

PubMed

Theil, Elizabeth C

2010-08-01

Cellular ferritin is central for iron balance during transfusions therapies; serum ferritin is a small fraction of body ferritin, albeit a convenient reporter. Iron overload induces extra ferritin protein synthesis but the protein is overfilled with the extra iron that damages ferritin, with conversion to toxic hemosiderin. Three new approaches that manipulate ferritin to address excess iron, hemosiderin, and associated oxidative damage in Cooley's Anemia and other iron overload conditions are faster removal of ferritin iron with chelators guided to ferritin gated pores by peptides; more ferritin protein synthesis using ferritin mRNA activators, by metal complexes that target mRNA 3D structures; and determining if endocytotic absorption of iron from legumes, which is mostly ferritin, is regulated during iron overload to prevent excess iron entry while providing protein. More of a focus on ferritin features, including protein cage structure, iron mineral, regulatable mRNA, and specific gut absorption properties, will achieve the three novel experimental goals for managing iron homeostasis with transfusion therapies.

Giant plasmonic energy and momentum transfer on the nanoscale

NASA Astrophysics Data System (ADS)

Durach, Maxim

We have developed a general theory of the plasmonic enhancement of many-body phenomena resulting in a closed expression for the surface plasmon-dressed Coulomb interaction. It is shown that this interaction has a resonant nature. We have also demonstrated that renormalized interaction is a long-ranged interaction whose intensity is considerably increased compared to bare Coulomb interaction over the entire region near the plasmonic nanostructure. We illustrate this theory by re-deriving the mirror charge potential near a metal sphere as well as the quasistatic potential behind the so-called perfect lens at the surface plasmon (SP) frequency. The dressed interaction for an important example of a metal--dielectric nanoshell is also explicitly calculated and analyzed. The renormalization and plasmonic enhancement of the Coulomb interaction is a universal effect, which affects a wide range of many-body phenomena in the vicinity of metal nanostructures: chemical reactions, scattering between charge carriers, exciton formation, Auger recombination, carrier multiplication, etc. We have described the nanoplasmonic-enhanced Forster resonant energy transfer (FRET) between quantum dots near a metal nanoshell. It is shown that this process is very efficient near high-aspect-ratio nanoshells. We have also obtained a general expression for the force exerted by an electromagnetic field on an extended polarizable object. This expression is applicable to a wide range of situations important for nanotechnology. Most importantly, this result is of fundamental importance for processes involving interaction of nanoplasmonic fields with metal electrons. Using the obtained expression for the force, we have described a giant surface-plasmon-induced drag-effect rectification (SPIDER), which exists under conditions of the extreme nanoplasmonic confinement. Under realistic conditions in nanowires, this giant SPIDER generates rectified THz potential differences up to 10V and extremely strong

Integrated System of Thermal/Dimensional Analysis for Quality Control of Metallic Melt and Ductile Iron Casting Solidification

NASA Astrophysics Data System (ADS)

Stan, Stelian; Chisamera, Mihai; Riposan, Iulian; Neacsu, Loredana; Cojocaru, Ana Maria; Stan, Iuliana

2018-03-01

The main objective of the present work is to introduce a specific experimental instrument and technique for simultaneously evaluating cooling curves and expansion or contraction of cast metals during solidification. Contraction/expansion analysis illustrates the solidification parameters progression, according to the molten cast iron characteristics, which are dependent on the melting procedure and applied metallurgical treatments, mold media rigidity and thermal behavior [heat transfer parameters]. The first part of the paper summarizes the performance of this two-mold device. Its function is illustrated by representative shrinkage tendency results in ductile cast iron as affected by mold rigidity (green sand and furan resin sand molds) and inoculant type (FeSi-based alloys), published in part previously. The second part of the paper illustrates an application of this equipment adapted for commercial foundry use. It conducts thermal analysis and volume change measurements in a single ceramic cup so that mold media as well as solidification conditions are constants, with cast iron quality as the variable. Experiments compared gray and ductile cast iron solidification patterns. Gray iron castings are characterized by higher undercooling at the beginning and at the end of solidification and lower graphitic expansion. Typically, ductile cast iron exhibits higher graphitic, initial expansion, conducive for shrinkage formation in soft molds.

Metallic multilayers at the nanoscale

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

Jankowski, A.F.

1994-11-01

The development of multilayer structures has been driven by a wide range of commercial applications requiring enhanced material behaviors. Innovations in physical vapor deposition technologies, in particular magnetron sputtering, have enabled the synthesis of metallic-based structures with nanoscaled layer dimensions as small as one-to-two monolayers. Parameters used in the deposition process are paramount to the Formation of these small layer dimensions and the stability of the structure. Therefore, optimization of the desired material properties must be related to assessment of the actual microstructure. Characterization techniques as x-ray diffraction and high resolution microscopy are useful to reveal the interface and layermore » structure-whether ordered or disordered crystalline, amorphous, compositionally abrupt or graded, and/or lattice strained Techniques for the synthesis of metallic multilayers with subnanometric layers will be reviewed with applications based on enhancing material behaviors as reflectivity and magnetic anisotropy but with emphasis on experimental studies of mechanical properties.« less

IRON INCREASES EXPRESSION OF IRON-EXPORT PROTEIN MTP1 IN LUNG CELLS

EPA Science Inventory

Accumulation of reactive iron in acute and chronic lung disease suggests that iron-driven free radical formation could contribute to tissue injury. Safe transport and sequestration of this metal is likely to be of importance in lung defense. We provide evidence for the expression...

Iron aluminide alloy coatings and joints, and methods of forming

DOEpatents

Wright, Richard N.; Wright, Julie K.; Moore, Glenn A.

1994-01-01

A method of joining two bodies together, at least one of the bodies being predominantly composed of metal, the two bodies each having a respective joint surface for joining with the joint surface of the other body, the two bodies having a respective melting point, includes the following steps: a) providing aluminum metal and iron metal on at least one of the joint surfaces of the two bodies; b) after providing the aluminum metal and iron metal on the one joint surface, positioning the joint surfaces of the two bodies in juxtaposition against one another with the aluminum and iron positioned therebetween; c) heating the aluminum and iron on the juxtaposed bodies to a temperature from greater than or equal to 600.degree. C. to less than the melting point of the lower melting point body; d) applying pressure on the juxtaposed surfaces; and e) maintaining the pressure and the temperature for a time period effective to form the aluminum and iron into an iron aluminide alloy joint which bonds the juxtaposed surfaces and correspondingly the two bodies together. The method can also effectively be used to coat a body with an iron aluminide coating.

Iron aluminide alloy coatings and joints, and methods of forming

DOEpatents

Wright, R.N.; Wright, J.K.; Moore, G.A.

1994-09-27

Disclosed is a method of joining two bodies together, at least one of the bodies being predominantly composed of metal, the two bodies each having a respective joint surface for joining with the joint surface of the other body, the two bodies having a respective melting point, includes the following steps: (a) providing aluminum metal and iron metal on at least one of the joint surfaces of the two bodies; (b) after providing the aluminum metal and iron metal on the one joint surface, positioning the joint surfaces of the two bodies in juxtaposition against one another with the aluminum and iron positioned therebetween; (c) heating the aluminum and iron on the juxtaposed bodies to a temperature from greater than or equal to 600 C to less than the melting point of the lower melting point body; (d) applying pressure on the juxtaposed surfaces; and (e) maintaining the pressure and the temperature for a time period effective to form the aluminum and iron into an iron aluminide alloy joint which bonds the juxtaposed surfaces and correspondingly the two bodies together. The method can also effectively be used to coat a body with an iron aluminide coating.

Metallic corrosion processes reactivation sustained by iron-reducing bacteria: Implication on long-term stability of protective layers

NASA Astrophysics Data System (ADS)

Esnault, L.; Jullien, M.; Mustin, C.; Bildstein, O.; Libert, M.

In deep geological environments foreseen for the disposal of radioactive waste, metallic containers will undergo anaerobic corrosion. In this context, the formation of corrosion products such as magnetite may reduce the rate of corrosion processes through the formation of a protective layer. This study aims at determining the direct impact of iron-reducing bacteria (IRB) activity on the stability of corrosion protective layers. Batch experiments investigating iron corrosion processes including the formation of secondary magnetite and its subsequent alteration in the presence of IRB show the bacteria ability to use structural Fe(III) for respiration which leads to the sustainment of a high corrosion rate. With the bio-reduction of corrosion products such as magnetite, and H 2 as electron donor, IRB promote the reactivation of corrosion processes in corrosive environments by altering the protective layer. This phenomenon could have a major impact on the long-term stability of metallic compounds involved in multi-barrier system for high-level radioactive waste containment.

Influence of permeability on nanoscale zero-valent iron particle transport in saturated homogeneous and heterogeneous porous media.

PubMed

Strutz, Tessa J; Hornbruch, Götz; Dahmke, Andreas; Köber, Ralf

2016-09-01

Nanoscale zero-valent iron (NZVI) particles can be used for in situ groundwater remediation. The spatial particle distribution plays a very important role in successful and efficient remediation, especially in heterogeneous systems. Initial sand permeability (k 0) influences on spatial particle distributions were investigated and quantified in homogeneous and heterogeneous systems within the presented study. Four homogeneously filled column experiments and a heterogeneously filled tank experiment, using different median sand grain diameters (d 50), were performed to determine if NZVI particles were transported into finer sand where contaminants could be trapped. More NZVI particle retention, less particle transport, and faster decrease in k were observed in the column studies using finer sands than in those using coarser sands, reflecting a function of k 0. In heterogeneous media, NZVI particles were initially transported and deposited in coarse sand areas. Increasing the retained NZVI mass (decreasing k in particle deposition areas) caused NZVI particles to also be transported into finer sand areas, forming an area with a relatively homogeneous particle distribution and converged k values despite the different grain sizes present. The deposited-particle surface area contribution to the increasing of the matrix surface area (θ) was one to two orders of magnitude higher for finer than coarser sand. The dependency of θ on d 50 presumably affects simulated k changes and NZVI distributions in numerical simulations of NZVI injections into heterogeneous aquifers. The results implied that NZVI can in principle also penetrate finer layers.

Hydrodechlorination of polychlorinated biphenyls in contaminated soil from an e-waste recycling area, using nanoscale zerovalent iron and Pd/Fe bimetallic nanoparticles.

PubMed

Chen, Xi; Yao, Xiaoyan; Yu, Chunna; Su, Xiaomei; Shen, Chaofeng; Chen, Chen; Huang, Ronglang; Xu, Xinhua

2014-04-01

Soil pollution by polychlorinated biphenyls (PCBs) arising from the crude disposal and recycling of electronic and electrical waste (e-waste) is a serious issue, and effective remediation technologies are urgently needed. Nanoscale zerovalent iron (nZVI) and bimetallic systems have been shown to promote successfully the destruction of halogenated organic compounds. In the present study, nZVI and Pd/Fe bimetallic nanoparticles synthesized by chemical deposition were used to remove 2,2',4,4',5,5'-hexachlorobiphenyl from deionized water, and then applied to PCBs contaminated soil collected from an e-waste recycling area. The results indicated that the hydrodechlorination of 2,2',4,4',5,5'-hexachlorobiphenyl by nZVI and Pd/Fe bimetallic nanoparticles followed pseudo-first-order kinetics and Pd loading was beneficial to the hydrodechlorination process. It was also found that the removal efficiencies of PCBs from soil achieved using Pd/Fe bimetallic nanoparticles were higher than that achieved using nZVI and that PCBs degradation might be affected by the soil properties. Finally, the potential challenges of nZVI application to in situ remediation were explored.

Air pollution particles and iron homeostasis | Science ...

EPA Pesticide Factsheets

Background: The mechanism underlying biological effects of particles deposited in the lung has not been defined. Major Conclusions: A disruption in iron homeostasis follows exposure of cells to all particulate matter including air pollution particles. Following endocytosis, functional groups at the surface of retained particle complex iron available in the cell. In response to a reduction in concentrations of requisite iron, a functional deficiency can result intracellularly. Superoxide production by the cell exposed to a particle increases ferrireduction which facilitates import of iron with the objective being the reversal of the metal deficiency. Failure to resolve the functional iron deficiency following cell exposure to particles activates kinases and transcription factors resulting in a release of inflammatory mediators and inflammation. Tissue injury is the end product of this disruption in iron homeostasis initiated by the particle exposure. Elevation of available iron to the cell precludes deficiency of the metal and either diminishes or eliminates biological effects.General Significance: Recognition of the pathway for biological effects after particle exposure to involve a functional deficiency of iron suggests novel therapies such as metal supplementation (e.g. inhaled and oral). In addition, the demonstration of a shared mechanism of biological effects allows understanding the common clinical, physiological, and pathological presentation fol

Recovery of Iron from Chromium Vanadium-Bearing Titanomagnetite Concentrate by Direct Reduction

NASA Astrophysics Data System (ADS)

Wang, Mingyu; Zhou, Shengfan; Wang, Xuewen; Chen, Bianfang; Yang, Haoxiang; Wang, Saikui; Luo, Pengfei

2016-10-01

The recovery of iron from chromium vanadium-bearing titanomagnetite concentrate was investigated by direct reduction, followed by magnetic separation. The results indicated that the metallization rate of iron can reach 98.9% at a temperature of 1200°C for a reduction duration of 60 min with the addition of 16% graphite powder and 0.5% sodium oxalate. Although the addition of borax, sodium carbonate and sodium oxalate to the chromium vanadium-bearing titanomagnetite concentrate can all improve the metallization rate of iron, the effect of sodium oxalate was the best. Sodium oxalate not only increases the metallization rate of iron but also promotes the growth of metallic iron. After magnetic separating, the recovery of iron was 92.8% and the iron content of magnetic concentrate was 88.4%.

Nanoscale rotary motors driven by electron tunneling.

PubMed

Wang, Boyang; Vuković, Lela; Král, Petr

2008-10-31

We examine by semiclassical molecular dynamics simulations the possibility of driving nanoscale rotary motors by electron tunneling. The model systems studied have a carbon nanotube shaft with covalently attached "isolating" molecular stalks ending with "conducting" blades. Periodic charging and discharging of the blades at two metallic electrodes maintains an electric dipole on the blades that is rotated by an external electric field. Our simulations demonstrate that these molecular motors can be efficient under load and in the presence of noise and defects.

Monomeric Yeast Frataxin is an Iron-Binding Protein

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

Cook,J.; Bencze, K.; Jankovic, A.

Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50 000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly)more » share requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

Monomeric Yeast Frataxin is an Iron Binding Protein†

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

Cook, J.; Bencze, K; Jankovic, A

Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly) sharemore » requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

Disruption of iron homeostasis and lung disease.

PubMed

Ghio, Andrew J

2009-07-01

As a result of a direct exchange with the external environment, the lungs are exposed to both iron and agents with a capacity to disrupt the homeostasis of this metal (e.g. particles). An increased availability of catalytically reactive iron can result from these exposures and, by generating an oxidative stress, this metal can contribute to tissue injury. By importing this Fe(3+) into cells for storage in a chemically less reactive form, the lower respiratory tract demonstrates an ability to mitigate both the oxidative stress presented by iron and its potential for tissue injury. This means that detoxification is accomplished by chemical reduction to Fe(2+) (e.g. by duodenal cytochrome b and other ferrireductases), iron import (e.g. by divalent metal transporter 1 and other transporters), and storage in ferritin. The metal can subsequently be exported from the cell (e.g. by ferroportin 1) in a less reactive state relative to that initially imported. Iron is then transported out of the lung via the mucociliary pathway or blood and lymphatic pathways to the reticuloendothelial system for long term storage. This coordinated handling of iron in the lung appears to be disrupted in several acute diseases on the lung including infections, acute respiratory distress syndrome, transfusion-related acute lung injury, and ischemia-reperfusion. Exposures to bleomycin, dusts and fibers, and paraquat similarly alter iron homeostasis in the lung to affect an oxidative stress. Finally, iron homeostasis is disrupted in numerous chronic lung diseases including pulmonary alveolar proteinosis, transplantation, cigarette smoking, and cystic fibrosis.

A Review of the Environmental Implications of in situ Remediation by Nanoscale Zero Valent Iron (nZVI): Behavior, Transport and Impacts on Microbial Communities

PubMed Central

Lefevre, Emilie; Bossa, Nathan; Wiesner, Mark R.; Gunsch, Claudia K.

2016-01-01

The increasing use of strategies incorporating nanoscale zero valent iron (nZVI) for soil and groundwater in situ remediation is raising some concerns regarding the potential adverse effects nZVI could have on indigenous microbial communities and ecosystem functioning. This review provides an overview of the current literature pertaining to the impacts of nZVI applications on microbial communities. Toxicity studies suggest that cell membrane disruption and oxidative stress through the generation of Fe2+ and reactive oxygen species by nZVI are the main mechanisms contributing to nZVI cytotoxicity. In addition, nZVI has been shown to substantially alter the taxonomic and functional composition of indigenous communities. However, because the physico-chemical conditions encountered in situ highly modulate nZVI toxicity, a better understanding of the environmental factors affecting nZVI toxicity and transport in the environment is of primary importance in evaluating the ecological consequences that could result from a more extensive use of nZVI. PMID:26897610

Complex-Morphology Metal-Based Nanostructures: Fabrication, Characterization, and Applications

PubMed Central

Gentile, Antonella; Ruffino, Francesco; Grimaldi, Maria Grazia

2016-01-01

Due to their peculiar qualities, metal-based nanostructures have been extensively used in applications such as catalysis, electronics, photography, and information storage, among others. New applications for metals in areas such as photonics, sensing, imaging, and medicine are also being developed. Significantly, most of these applications require the use of metals in the form of nanostructures with specific controlled properties. The properties of nanoscale metals are determined by a set of physical parameters that include size, shape, composition, and structure. In recent years, many research fields have focused on the synthesis of nanoscale-sized metallic materials with complex shape and composition in order to optimize the optical and electrical response of devices containing metallic nanostructures. The present paper aims to overview the most recent results—in terms of fabrication methodologies, characterization of the physico-chemical properties and applications—of complex-morphology metal-based nanostructures. The paper strongly focuses on the correlation between the complex morphology and the structures’ properties, showing how the morphological complexity (and its nanoscale control) can often give access to a wide range of innovative properties exploitable for innovative functional device production. We begin with an overview of the basic concepts on the correlation between structural and optical parameters of nanoscale metallic materials with complex shape and composition, and the possible solutions offered by nanotechnology in a large range of applications (catalysis, electronics, photonics, sensing). The aim is to assess the state of the art, and then show the innovative contributions that can be proposed in this research field. We subsequently report on innovative, versatile and low-cost synthesis techniques, suitable for providing a good control on the size, surface density, composition and geometry of the metallic nanostructures. The main

Surface modification of traditional and bioresorbable metallic implant materials for improved biocompatibility

NASA Astrophysics Data System (ADS)

Walker, Emily K.

Due to their strength, elasticity, and durability, a variety of metal alloys are commonly used in medical implants. Traditionally, corrosion-resistant metals have been preferred. These permanent materials can cause negative systemic and local tissue effects in the long-term. Permanent stenting can lead to late-stent thrombosis and in-stent restenosis. Metallic pins and screws for fracture fixation can corrode and fail, cause loss of bone mass, and contribute to inflammation and pain at the implant site, requiring reintervention. Corrodible metallic implants have the potential to prevent many of these complications by providing transient support to the affected tissue, dissolving at a rate congruent with the healing of the tissue. Alloys of iron and manganese (FeMn) exhibit similar fatigue strength, toughness, and elasticity compared with 316L stainless steel, making them very attractive candidates for bioresorbable stents and temporary fracture fixation devices. Much attention in recent years has been given to creating alloys with ideal mechanical properties for various applications. Little work has been done on determining the blood compatibility of these materials or on examining how their surfaces can be improved to improve cell adhesion, however. We examined thethrombogenic response of blood exposed to various resorbable ferrous stent materials through contact with porcine blood. The resorbable materials induced comparable or lower levels of several coagulation factors compared with 316L stainless steel. Little platelet adhesion was observed on any of the tested materials. Endothelialization is an important process after the implantation of a vascular stent, as it prevents damage to the vessel wall that can accelerate neointimal hyperplasia. Micromotion can lead to the formation of fibrous tissue surrounding an orthopedic implant, loosening, and ultimately failure of the implant. Nanoscale features were created on the surfaces of noble metal coatings, silicon

Three-dimensional coherent x-ray diffraction imaging of molten iron in mantle olivine at nanoscale resolution.

PubMed

Jiang, Huaidong; Xu, Rui; Chen, Chien-Chun; Yang, Wenge; Fan, Jiadong; Tao, Xutang; Song, Changyong; Kohmura, Yoshiki; Xiao, Tiqiao; Wang, Yong; Fei, Yingwei; Ishikawa, Tetsuya; Mao, Wendy L; Miao, Jianwei

2013-05-17

We report quantitative 3D coherent x-ray diffraction imaging of a molten Fe-rich alloy and crystalline olivine sample, synthesized at 6 GPa and 1800 °C, with nanoscale resolution. The 3D mass density map is determined and the 3D distribution of the Fe-rich and Fe-S phases in the olivine-Fe-S sample is observed. Our results indicate that the Fe-rich melt exhibits varied 3D shapes and sizes in the olivine matrix. This work has potential for not only improving our understanding of the complex interactions between Fe-rich core-forming melts and mantle silicate phases but also paves the way for quantitative 3D imaging of materials at nanoscale resolution under extreme pressures and temperatures.

Nanoscale Insight and Control of Structural and Electronic Properties of Organic Semiconductor / Metal Interfaces

NASA Astrophysics Data System (ADS)

Maughan, Bret

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial

Nanostructured metal-polyaniline composites

DOEpatents

Wang, Hsing-Lin; Li, Wenguang; Bailey, James A.; Gao, Yuan

2010-08-31

Metal-polyaniline (PANI) composites are provided together with a process of preparing such composites by an electrodeless process. The metal of the composite can have nanoscale structural features and the composites can be used in applications such as catalysis for hydrogenation reactions and for analytical detection methods employing SERS.

ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

PubMed Central

Razzell, W. E.; Trussell, P. C.

1963-01-01

Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

Method for producing electrodes using microscale or nanoscale materials obtained from hydrogendriven metallurgical reactions

DOEpatents

Reilly, James J.; Adzic, Gordana D.; Johnson, John R.; Vogt, Thomas; McBreen, James

2003-09-02

A method is provided for producing electrodes using microscale and nanoscale metal materials formed from hydrogen driven metallurgical processes; such a the HD (hydriding, dehydriding) process, the HDDR (hydriding, dehydriding, disproportionation, and recombination) process, and variants thereof.

Iron and aluminium oxides containing industrial wastes as adsorbents of heavy metals: Application possibilities and limitations.

PubMed

Jacukowicz-Sobala, Irena; Ociński, Daniel; Kociołek-Balawejder, Elżbieta

2015-07-01

Industrial wastes with a high iron or aluminium oxide content are produced in huge quantities as by-products of water treatment (water treatment residuals), bauxite processing (red mud) and hard and brown coal burning in power plants (fly ash). Although they vary in their composition, the wastes have one thing in common--a high content of amorphous iron and/or aluminium oxides with a large specific surface area, whereby this group of wastes shows very good adsorbability towards heavy metals, arsenates, selenates, etc. But their physical form makes their utilisation quite difficult, since it is not easy to separate the spent sorbent from the solution and high bed hydraulic resistances occur in dynamic regime processes. Nevertheless, because of the potential benefits of utilising the wastes in industrial effluent treatment, this issue attracts much attention today. This study describes in detail the waste generation processes, the chemical structure of the wastes, their physicochemical properties, and the mechanisms of fixing heavy metals and semimetals on the surface of iron and aluminium oxides. Typical compositions of wastes generated in selected industrial plants are given. A detailed survey of the literature on the adsorption applications of the wastes, including methods of their thermal and chemical activation, as well as regeneration of the spent sorbents, is presented. The existing and potential ways of modifying the physical form of the discussed group of wastes, making it possible to overcome the basic limitation on their practical use, are discussed. © The Author(s) 2015.

Metal-metal bond lengths in complexes of transition metals.

PubMed

Pauling, L

1976-12-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

The application of illite supported nanoscale zero valent iron for the treatment of uranium contaminated groundwater.

PubMed

Jing, C; Landsberger, S; Li, Y L

2017-09-01

In this study, nanoscale zero valent iron I-NZVI was investigated as a remediation strategy for uranium contaminated groundwater from the former Cimarron Fuel Fabrication Site in Oklahoma, USA. The 1 L batch-treatment system was applied in the study. The result shows that 99.9% of uranium in groundwater was removed by I-NZVI within 2 h. Uranium concentration in the groundwater stayed around 27 μg/L, and there was no sign of uranium release into groundwater after seven days of reaction time. Meanwhile the release of iron was significantly decreased compared to NZVI which can reduce the treatment impact on the water environment. To study the influence of background pH of the treatment system on removal efficiency of uranium, the groundwater was adjusted from pH 2-10 before the addition of I-NZVI. The pH of the groundwater was from 2.1 to 10.7 after treatment. The removal efficiency of uranium achieved a maximum in neutral pH of groundwater. The desorption of uranium on the residual solid phase after treatment was investigated in order to discuss the stability of uranium on residual solids. After 2 h of leaching, 0.07% of the total uranium on residual solid phase was leached out in a HNO 3 leaching solution with a pH of 4.03. The concentration of uranium in the acid leachate was under 3.2 μg/L which is below the EPA's maximum contaminant level of 30 μg/L. Otherwise, the concentration of uranium was negligible in distilled water leaching solution (pH = 6.44) and NaOH leaching solution (pH = 8.52). A desorption study shows that an acceptable amount of uranium on the residuals can be released into water system under strong acid conditions in short terms. For long term disposal management of the residual solids, the leachate needs to be monitored and treated before discharge into a hazardous landfill or the water system. For the first time, I-NZVI was applied for the treatment of uranium contaminated groundwater. These results provide proof that I-NZVI has

Transition metals at the host–pathogen interface: How Neisseria exploit human metalloproteins for acquiring iron and zinc

PubMed Central

Neumann, Wilma; Hadley, Rose C.; Nolan, Elizabeth M.

2017-01-01

Transition metals are essential nutrients for all organisms and important players in the host-microbe interaction. During bacterial infection, a tug-of-war between the host and microbe for nutrient metals occurs: the host innate immune system responds to the pathogen by reducing metal availability and the pathogen tries to outmaneuver this response. The outcome of this competition, which involves metal-sequestering host-defense proteins and microbial metal acquisition machinery, is an important variable for whether infection occurs. One strategy bacterial pathogens employ to overcome metal restriction involves hijacking abundant host metalloproteins. The obligate human pathogens Neisseria spp. express TonB-dependent transport systems that capture human metalloproteins, extract the bound metal ions, and deliver these nutrients into the bacterial cell. This Essay highlights structural and mechanistic investigations that provide insights into how Neisseria acquire iron from the Fe(III)-transport protein transferrin, the Fe(III)-chelating host-defense protein lactoferrin, and the oxygen-transport protein hemoglobin, and obtain zinc from the metal-sequestering antimicrobial protein calprotectin. PMID:28487398

Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases.

PubMed

Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao; Chen, Zhuqi; Wu, Kangbing; Yin, Guochuan

2015-06-07

Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like Zn(2+) through a plausible chloride or OTf(-) bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Root, Robert A.; Hayes, Sarah M.; Hammond, Corin M.; Maier, Raina M.; Chorover, Jon

2015-01-01

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe

Rapid decolorization of textile wastewater by green synthesized iron nanoparticles.

PubMed

Ozkan, Z Y; Cakirgoz, M; Kaymak, E S; Erdim, E

2018-01-01

The effectiveness of green tea (Camellia sinensis) and pomegranate (Punica granatum) extracts for the production of iron nanoparticles and their application for color removal from a textile industry wastewater was investigated. Polyphenols in extracts act as reducing agents for iron ions in aqueous solutions, forming iron nanoparticles. Pomegranate extract was found to have almost a 10-fold higher polyphenolic content than the same amount of green tea extract on a mass basis. However, the size of the synthesized nanoparticles did not show a correlation with the polyphenolic content. 100 ppm and 300 ppm of iron nanoparticles were evaluated in terms of color removal efficiency from a real textile wastewater sample. 300 ppm of pomegranate nanoscale zero-valent iron particles showed more than 95% color removal and almost 80% dissolved organic carbon removal. The degradation mechanisms are is considered to be adsorption and precipitation to a major extent, and mineralization to a minor extent.

Biogeochemistry: Deep ocean iron balance

NASA Astrophysics Data System (ADS)

Homoky, William B.

2017-02-01

Dissolved iron is mysteriously pervasive in deep ocean hydrothermal plumes. An analysis of gas, metals and particles from a 4,000 km plume transect suggests that dissolved iron is maintained by rapid and reversible exchanges with sinking particles.

Enhanced sequestration of Cr(VI) by nanoscale zero-valent iron supported on layered double hydroxide by batch and XAFS study.

PubMed

Sheng, Guodong; Hu, Jun; Li, Hui; Li, Jiaxing; Huang, Yuying

2016-04-01

Herein, the reduction of nanoscale zero-valent iron (NZVI) and adsorption of layered double hydroxides (LDH) to sequester Cr(VI) were well combined by the immobilization of NZVI onto LDH surface (NZVI/LDH). The characterization results revealed that LDH decreased NZVI aggregation and thus increased Cr(VI) sequestration. The batch results indicated that Cr(VI) sequestration by NZVI/LDH was higher than that of NZVI, and superior to the sum of reduction and adsorption. The LDH with good anion exchange property allowed the adsorption of Cr(VI), facilitating interfacial reaction by increasing the local concentration of Cr(VI) in the NZVI vicinity. X-ray absorption near edge structure (XANES) results indicated that Cr(VI) was almost completely reduced to Cr(III) by NZVI/LDH, but Cr(VI) was partly reduced to Cr(III) by NZVI with a trace of Cr(VI) adsorbed on corrosion products. The coordination environment of Cr from extended X-ray absorption fine structure (EXAFS) analysis revealed that LDH could be a good scavenger for the insoluble products produced during reaction. So, the insoluble products on NZVI could be reduced, and its reactivity could be maintained. These results demonstrated that NZVI/LDH exhibits multiple functionalities relevant to the remediation of Cr(VI)-contaminated sites. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mineral resource of the month: Iron and steel

USGS Publications Warehouse

Fenton, Michael D.

2014-01-01

Iron is one of the most abundant elements on Earth, but it does not occur in nature in a useful metallic form. Although ancient people may have recovered some iron from meteorites, it wasn’t until smelting was invented that iron metal could be derived from iron oxides. After the beginning of the Iron Age in about 1200 B.C., knowledge of iron- and steelmaking spread from the ancient Middle East through Greece to the Roman Empire, then to Europe and, in the early 17th century, to North America. The first successful furnace in North America began operating in 1646 in what is now Saugus, Mass. Introduction of the Bessemer converter in the mid-19th century made the modern steel age possible.

Metal Tolerance Protein 8 Mediates Manganese Homeostasis and Iron Reallocation during Seed Development and Germination1[OPEN

PubMed Central

Takahashi, Michiko; Terada, Yasuko

2017-01-01

Metal accumulation in seeds is a prerequisite for germination and establishment of plants but also for micronutrient delivery to humans. To investigate metal transport processes and their interactions in seeds, we focused on METAL TOLERANCE PROTEIN8 (MTP8), a tonoplast transporter of the manganese (Mn) subclade of cation diffusion facilitators, which in Arabidopsis (Arabidopsis thaliana) is expressed in embryos of seeds. The x-ray fluorescence imaging showed that expression of MTP8 was responsible for Mn localization in subepidermal cells on the abaxial side of the cotyledons and in cortical cells of the hypocotyl. Accordingly, under low Mn availability, MTP8 increased seed stores of Mn, required for efficient seed germination. In mutant embryos lacking expression of VACUOLAR IRON TRANSPORTER1 (VIT1), MTP8 built up iron (Fe) hotspots in MTP8-expressing cells types, suggesting that MTP8 transports Fe in addition to Mn. In mtp8 vit1 double mutant seeds, Mn and Fe were distributed in all cell types of the embryo. An Fe transport function of MTP8 was confirmed by its ability to complement Fe hypersensitivity of a yeast mutant defective in vacuolar Fe transport. Imbibing mtp8-1 mutant seeds in the presence of Mn or subjecting seeds to wet-dry cycles showed that MTP8 conferred Mn tolerance. During germination, MTP8 promoted reallocation of Fe from the vasculature. These results indicate that cell type-specific accumulation of Mn and Fe in seeds depends on MTP8 and that this transporter plays an important role in the generation of seed metal stores as well as for metal homeostasis and germination efficiency under challenging environmental conditions. PMID:28461400

Synthesis, Microstructure and Properties of Metallic Materials with Nanoscale Growth Twins

DTIC Science & Technology

2006-11-01

2004: Wu et al, 2005) and austenitic stainless steels (Zhang et al, 2004a; Zhang et al, 2005). However, processing routes to produce nanoscale...mechanical properties (hardness, yield strength, tensile strength) of bulk austenitic stainless steel (304, 310, 316 and 330) are quite similar and...model developed for the formation of growth twins in sputter- deposited austenitic stainless steel thin films (Zhang et al, 2004b). The model predicts

Surprising abundance of Gallionella-related iron oxidizers in creek sediments at pH 4.4 or at high heavy metal concentrations

USGS Publications Warehouse

Fabisch, Maria; Beulig, Felix; Akob, Denise M.; Küsel, Kirsten

2013-01-01

We identified and quantified abundant iron-oxidizing bacteria (FeOB) at three iron-rich, metal-contaminated creek sites with increasing sediment pH from extremely acidic (R1, pH 2.7), to moderately acidic (R2, pH 4.4), to slightly acidic (R3, pH 6.3) in a former uranium-mining district. The geochemical parameters showed little variations over the 1.5 year study period. The highest metal concentrations found in creek sediments always coincided with the lowest metal concentrations in creek water at the slightly acidic site R3. Sequential extractions of R3 sediment revealed large portions of heavy metals (Ni, Cu, Zn, Pb, U) bound to the iron oxide fraction. Light microscopy of glass slides exposed in creeks detected twisted stalks characteristic of microaerobic FeOB of the family Gallionellaceae at R3 but also at the acidic site R2. Sequences related to FeOB such as Gallionella ferruginea, Sideroxydans sp. CL21, Ferritrophicum radicicola, and Acidovorax sp. BrG1 were identified in the sediments. The highest fraction of clone sequences similar to the acidophilic “Ferrovum myxofaciens” was detected in R1. Quantitative PCR using primer sets specific for Gallionella spp., Sideroxydans spp., and “Ferrovum myxofaciens” revealed that ~72% (R2 sediment) and 37% (R3 sediment) of total bacterial 16S rRNA gene copies could be assigned to groups of FeOB with dominance of microaerobic Gallionella spp. at both sites. Gallionella spp. had similar and very high absolute and relative gene copy numbers in both sediment communities. Thus, Gallionella-like organisms appear to exhibit a greater acid and metal tolerance than shown before. Microaerobic FeOB from R3 creek sediment enriched in newly developed metal gradient tubes tolerated metal concentrations of 35 mM Co, 24 mM Ni, and 1.3 mM Cd, higher than those in sediments. Our results will extend the limited knowledge of FeOB at contaminated, moderately to slightly acidic environments.

Changes of the corrosion potential of iron in stagnation and flow conditions and their relationship with metal release.

PubMed

Fabbricino, Massimiliano; Korshin, Gregory V

2014-10-01

This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water during episodes of stagnation and flow. These measurements showed that during stagnation episodes, Ecorr values decrease prominently and consistently. This decrease is initially rapid but it becomes slower as the stagnation time increases. During flow episodes, the Ecorr values increase and reach a quasi-steady state. Experiments with varying concentrations of dissolved oxygen showed that the decrease of Ecorr values characteristic for stagnation is likely to be associated with the consumption of dissolved oxygen by the exposed metal. The corrosion potential of iron and its changes during stagnation were sensitive to the concentrations of sulfate and chloride ions. Measurements of iron release showed that both the absolute values of Ecorr measured prior to or after stagnation episodes were well correlated with the logarithms of concentrations of total iron. The slope of this dependence showed that the observed correlations between Ecorr values and Fe concentrations corresponded to the coupling between the oxidant consumption and changes of Fe redox status. These results demonstrate that in situ Ecorr measurements can be a sensitive method with which to ascertain effects of hydrodynamic conditions and short-term variations of water chemistry on metal release and corrosion in drinking water. This approach is valuable practically because Ecorr measurements are precise, can be carried out in situ with any desired time resolution, do not affect the state of exposed surface in any extent and can be carried out with readily available equipment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cytosolic iron chaperones: Proteins delivering iron cofactors in the cytosol of mammalian cells.

PubMed

Philpott, Caroline C; Ryu, Moon-Suhn; Frey, Avery; Patel, Sarju

2017-08-04

Eukaryotic cells contain hundreds of metalloproteins that are supported by intracellular systems coordinating the uptake and distribution of metal cofactors. Iron cofactors include heme, iron-sulfur clusters, and simple iron ions. Poly(rC)-binding proteins are multifunctional adaptors that serve as iron ion chaperones in the cytosolic/nuclear compartment, binding iron at import and delivering it to enzymes, for storage (ferritin) and export (ferroportin). Ferritin iron is mobilized by autophagy through the cargo receptor, nuclear co-activator 4. The monothiol glutaredoxin Glrx3 and BolA2 function as a [2Fe-2S] chaperone complex. These proteins form a core system of cytosolic iron cofactor chaperones in mammalian cells. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Viability of a nanoremediation  process in single or multi-metal(loid) contaminated soils.

PubMed

Gil-Díaz, M; Pinilla, P; Alonso, J; Lobo, M C

2017-01-05

The effectiveness of single- and multi-metal(loid) immobilization of As, Cd, Cr, Pb and Zn using different doses of nanoscale zero-valent iron (nZVI) was evaluated and compared in two different soils, a calcareous and an acidic one. The effectiveness of nZVI to immobilize metal(loid)s in soil strongly depended on the metal characteristics, soil properties, dose of nZVI and presence of other metal(loid)s. In the case of single contamination, this nanoremediation strategy was effective for all of the metal(loid)s studied except for Cd. When comparing the two soils, anionic metal(loid)s (As and Cr) were more easily retained in acidic soil, whereas cationic metal(loid)s (Cd, Pb and Zn), were immobilized more in calcareous soil. In multi-metal(loid) contaminated soils, the presence of several metal(loid)s affected their immobilization, which was probably due to the competitive phenomenon between metal(loid) ions, which can reduce their sorption or produce synergistic effects. At 10% of nZVI, As, Cr and Pb availability decreased more than 82%, for Zn it ranged between 31 and 75% and for Cd between 13 and 42%. Thus, the application of nZVI can be a useful strategy to immobilize As, Cr, Pb and Zn in calcareous or acidic soils in both single- or multi-metal(loid) contamination conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Nano-scale zero valent iron transport in a variable aperture dolomite fracture and a glass fracture

NASA Astrophysics Data System (ADS)

Mondal, P.; Sleep, B. E.; Cui, Z.; Zhou, Z.

2014-12-01

Experiments and numerical simulations are being performed to understand the transport behavior of carboxymethyl cellulose polymer stabilized nano-scale zero valent iron (nZVI) in a variable aperture dolomite rock fracture and a variable aperture glass replica of a fractured slate. The rock fracture was prepared by artificially inducing a fracture in a dolomite block along a stylolite, and the glass fracture was prepared by creating molds with melted glass on two opposing sides of a fractured slate rock block. Both of the fractures were 0.28 m in length and 0.21 m in width. Equivalent hydraulic apertures are about 110 microns for the rock fracture and 250 microns for the glass replica fracture. Sodium bromide and lissamine green B (LGB) serve as conservative tracers in the rock fracture and glass replica fracture, respectively. A dark box set-up with a light source and digital camera is being used to visualize the LGB and CMC-nZVI movement in the glass fracture. Experiments are being performed to determine the effects of water specific discharge and CMC concentration on nZVI transport in the fractures. Transmission electron microscopy, dynamic light scattering, and UV-visual spectrophotometry were performed to determine the stability and characteristics of the CMC-nZVI mixture. The transport of bromide, LGB, CMC, and CMC-nZVI in both fractures is being evaluated through analysis of the effluent concentrations. Time-lapse images are also being captured for the glass fracture. Bromide, LGB, and CMC recoveries have exceeded 95% in both fractures. Significant channeling has been observed in the fractures for CMC transport due to viscous effects.

Chemical classification of iron meteorites. XI - Multi-element studies of 38 new irons and the high abundance of ungrouped irons from Antarctica

NASA Technical Reports Server (NTRS)

Wasson, John T.; Ouyang, Xinwei; Wang, Jianmin; Jerde, Eric

1989-01-01

Concentrations of 14 elements in the metal of 38 iron meteorites and a pallasite are reported. Three samples are paired with previously classified irons, raising the number of well-classified, independent iron meteorites to 598. Several of the new irons are from Antarctica. Of 24 independent irons from Antarctica, eight are ungrouped, a much higher fraction than that among all classified irons. The difference is probably related to the fact that the median mass of Antarctic irons is about two orders of magnitude smaller than that of non-Antarctic irons. Smaller meteoroids may tend to sample a larger number of asteroidal source regions, perhaps because small meteoroids tend to have higher ejection velocities or because they have random-walked a greater increment of orbital semimajor axis away from that of the parent body.

Association of the sites of heavy metals with nanoscale carbon in a Kentucky electrostatic precipitator fly ash

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

James C. Hower; Uschi M. Graham; Alan Dozier

2008-11-15

A combination of high-resolution transmission electron microscopy, scanning transmission electron microscopy, and electron energy-loss spectroscopy (HRTEM-STEM-EELS) was used to study fly ashes produced from the combustion of an eastern Kentucky coal at a southeastern-Kentucky wall-fired pulverized coal utility boiler retrofitted for low-NOx combustion. Fly ash was collected from individual hoppers in each row of the electrostatic precipitators (ESP) pollution-control system, with multiple hoppers sampled within each of the three rows. Temperatures within the ESP array range from about 200 {degree}C at the entry to the first row to <150{degree}C at the exit of the third row. HRTEM-STEM-EELS study demonstrated themore » presence of nanoscale (10 s nm) C agglomerates with typical soot-like appearance and others with graphitic fullerene-like nanocarbon structures. The minute carbon agglomerates are typically juxtaposed and intergrown with slightly larger aluminosilicate spheres and often form an ultrathin halo or deposit on the fly ash particles. The STEM-EELS analyses revealed that the nanocarbon agglomerates host even finer (<3 nm) metal and metal oxide particles. Elemental analysis indicated an association of Hg with the nanocarbon. Arsenic, Se, Pb, Co, and traces of Ti and Ba are often associated with Fe-rich particles within the nanocarbon deposits. 57 refs., 5 figs.« less

Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology.

PubMed

Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

2015-01-01

Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail.

Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology

PubMed Central

Skjørringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

2015-01-01

Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail. PMID:26106291

Simultaneous removal of cadmium and nitrate in aqueous media by nanoscale zerovalent iron (nZVI) and Au doped nZVI particles.

PubMed

Su, Yiming; Adeleye, Adeyemi S; Huang, Yuxiong; Sun, Xiaoya; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei; Keller, Arturo A

2014-10-15

Nanoscale zerovalent iron (nZVI) has demonstrated high efficacy for treating nitrate or cadmium (Cd) contamination, but its efficiency for simultaneous removal of nitrate and Cd has not been investigated. This study evaluated the reactivity of nZVI to the co-contaminants and by-product formation, employed different catalysts to reduce nitrite yield from nitrate, and examined the transformation of nZVI after reaction. Nitrate reduction resulted in high solution pH, negatively charged surface of nZVI, formation of Fe3O4 (a stable transformation of nZVI), and no release of ionic iron. Increased pH and negative charge contributed to significant increase in Cd(II) removal capacity (from 40 mg/g to 188 mg/g) with nitrate present. In addition, nitrate reduction by nZVI could be catalyzed by Cd(II): while 30% of nitrate was reduced by nZVI within 2 h in the absence of Cd(II), complete nitrate reduction was observed in the presence of 40 mg-Cd/L due to the formation of Cd islands (Cd(0) and CdO) on the nZVI particles. While nitrate was reduced mostly to ammonium when Cd(II) was not present or at Cd(II) concentrations ≥ 40 mg/L, up to 20% of the initial nitrate was reduced to nitrite at Cd(II) concentrations < 40 mg/L. Among nZVI particles doped with 1 wt. % Cu, Ag, or Au, nZVI deposited with 1 wt. % Au reduced nitrite yield to less than 3% of the initial nitrate, while maintaining a high Cd(II) removal capacity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Metal-metal bond lengths in complexes of transition metals*

PubMed Central

Pauling, Linus

1976-01-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

Recent applications of liquid metals featuring nanoscale surface oxides

NASA Astrophysics Data System (ADS)

Neumann, Taylor V.; Dickey, Michael D.

2016-05-01

This proceeding describes recent efforts from our group to control the shape and actuation of liquid metal. The liquid metal is an alloy of gallium and indium which is non-toxic, has negligible vapor pressure, and develops a thin, passivating surface oxide layer. The surface oxide allows the liquid metal to be patterned and shaped into structures that do not minimize interfacial energy. The surface oxide can be selectively removed by changes in pH or by applying a voltage. The surface oxide allows the liquid metal to be 3D printed to form free-standing structures. It also allows for the liquid metal to be injected into microfluidic channels and to maintain its shape within the channels. The selective removal of the oxide results in drastic changes in surface tension that can be used to control the flow behavior of the liquid metal. The metal can also wet thin, solid films of metal that accelerates droplets of the liquid along the metal traces .Here we discuss the properties and applications of liquid metal to make soft, reconfigurable electronics.

Short-term effects of nanoscale Zero-Valent Iron (nZVI) and hydraulic shock during high-rate anammox wastewater treatment.

PubMed

Xu, Jia-Jia; Zhang, Zheng-Zhe; Ji, Zheng-Quan; Zhu, Ying-Hong; Qi, Si-Yu; Tang, Chong-Jian; Jin, Ren-Cun

2018-06-01

The stability and resilience of an anaerobic ammonium oxidation (anammox) system under transient nanoscale Zero-Valent Iron (nZVI) (50, 75 and 100 mg L -1 ), hydraulic shock (2-fold increase in flow rate) and their combination were studied in an up-flow anaerobic sludge blanket reactor. The response to the shock loads can be divided into three phases i.e. shock, inertial and recovery periods. The effects of the shock loads were directly proportional to the shock intensity. The effluent quality was gradually deteriorated after exposure to high nZVI level (100 mg L -1 ) for 2 h. The higher effluent sensitivity index and response caused by unit intensity of shock was observed under hydraulic and combined shocks. Notably, the specific anammox activity and the content of heme c were considerably reduced during the shock phase and the maximum loss rates were about 30.5% and 24.8%, respectively. Nevertheless, the extracellular polymeric substance amount in the shock phase was enhanced in varying degrees and variation tendency was disparate at all the tested shock loads. These results suggested that robustness of the anammox system was dependent on the magnitude shocks applied and the reactor resistance can be improved by reducing hydraulic retention time with the increase of nZVI concentration under these circumstances. Copyright © 2018 Elsevier Ltd. All rights reserved.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

A nanoscale Zr-based fluorescent metal-organic framework for selective and sensitive detection of hydrogen sulfide

NASA Astrophysics Data System (ADS)

Li, Yanping; Zhang, Xin; Zhang, Ling; Jiang, Ke; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2017-11-01

Hydrogen sulfide (H2S) has been commonly viewed as a gas signaling molecule in various physiological and pathological processes. However, the highly efficient H2S detection still remains challenging. Herein, we designed a new robust nano metal-organic framework (MOF) UiO-66-CH=CH2 as a fluorescent probe for rapid, sensitive and selective detection of biological H2S. UiO-66-CH=CH2 was prepared by heating ZrCl4 and 2-vinylterephthalic acid via a simple method. UiO-66-CH=CH2 displayed fluorescence quenching to H2S and kept excellent selectivity in the presence of biological relevant analytes especially the cysteine and glutathione. This MOF-based probe also exhibited fast response (10 s) and high sensitivity with a detection limit of 6.46 μM which was within the concentration range of biological H2S in living system. Moreover, this constructed MOF featured water-stability, nanoscale (20-30 nm) and low toxicity, which made it a promising candidate for biological H2S sensing.