Sulfur-Modified Zero-Valent Iron for Remediation Applications at DOE Sites - 13600

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

Fogwell, Thomas W.; Santina, Pete

2013-07-01

Many DOE remediation sites have chemicals of concern that are compounds in higher oxidation states, which make them both more mobile and more toxic. The chemical reduction of these compounds both prevents the migration of these chemicals and in some cases reduces the toxicity. It has also been shown that zero-valent iron is a very effective substance to use in reducing oxygenated compounds in various treatment processes. These have included the treatment of halogenated hydrocarbons in the form volatile organic compounds used as solvents and pesticides. Zero-valent iron has also been used to reduce various oxidized metals such as chromium,more » arsenic, and mercury in order to immobilize them, decrease their toxicity, and prevent further transport. In addition, it has been used to immobilize or break down other non-metallic species such as selenium compounds and nitrates. Of particular interest at several DOE remediation sites is the fact that zero-valent iron is very effective in immobilizing several radioactive metals which are mobile in their oxidized states. These include both technetium and uranium. The main difficulty in using zero-valent iron has been its tendency to become inactive after relatively short periods of time. While it is advantageous to have the zero-valent iron particles as porous as possible in order to provide maximum surface area for reactions to take place, these pores can become clogged when the iron is oxidized. This is due to the fact that ferric oxide has a greater volume for a given mass than metallic iron. When the surfaces of the iron particles oxidize to ferric oxide, the pores become narrower and will eventually shut. In order to minimize the degradation of the chemical activity of the iron due to this process, a modification of zero-valent iron has been developed which prevents or slows this process, which decreases its effectiveness. It is called sulfur-modified iron, and it has been produced in high purity for applications in municipal water treatment applications. Sulfur-modified iron has been found to not only be an extremely economical treatment technology for municipal water supplies, where very large quantities of water must be treated economically, but it has also been demonstrated to immobilize technetium. It has the added benefit of eliminating several other harmful chemicals in water supplies. These include arsenic and selenium. In one large-scale evaluation study an integrated system implemented chemical reduction of nitrate with sulfur-modified iron followed by filtration for arsenic removal. The sulfur-modified iron that was used was an iron-based granular medium that has been commercially developed for the removal of nitrate, co-contaminants including uranium, vanadium and chromium, and other compounds from water. The independent study concluded that 'It is foreseen that the greatest benefit of this technology (sulfur-modified iron) is that it does not produce a costly brine stream as do the currently accepted nitrate removal technologies of ion exchange and reverse osmosis. This investigation confirmed that nitrate reduction via sulfur-modified iron is independent of the hydraulic loading rate. Future sulfur-modified iron treatment systems can be designed without restriction of the reactor vessel dimensions. Future vessels can be adapted to existing site constraints without being limited to height-to-width ratios that would exist if nitrate reduction were to depend on hydraulic loading rate'. Sulfur-modified iron was studied by the Pacific Northwest National Laboratory (PNNL) for its effectiveness in the reduction and permanent sequestration of technetium. The testing was done using Hanford Site groundwater together with sediment. The report stated, 'Under reducing conditions, TcO{sub 4} is readily reduced to TcIV, which forms highly insoluble oxides such at TcO{sub 2}.nH{sub 2}O. However, (re)oxidation of TcIV oxides can lead to remobilization. Under sulfidogenic conditions, most TcIV will be reduced and immobilized as Tc{sub 2}S{sub 7}, which is less readily re-mobilized, even under oxic conditions. This process should be favored by stimulation of sulfidogenic conditions'. The sulfur-modified iron provides the sulfur, together with the iron, to maintain this stable sequestration of technetium. As a result of these and other studies demonstrating the cost-effectiveness of sulfur-modified iron in treating technetium and other hazardous compounds in Hanford Site groundwater and its cost-effectiveness in reducing nitrate, the Richland Operations Office of the Department of Energy issued a change order to the Central Plateau Contractor providing for the testing of sulfur-modified iron in a mobile pilot unit at the Hanford Site. Further testing is anticipated to produce refinements in operating conditions and further optimization of the existing process. (authors)« less

Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments

PubMed Central

Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W.; Conrad, Ralf; Kamagata, Yoichi

2015-01-01

Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8–98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides. PMID:25999927

Isolation of microorganisms involved in reduction of crystalline iron(III) oxides in natural environments.

PubMed

Hori, Tomoyuki; Aoyagi, Tomo; Itoh, Hideomi; Narihiro, Takashi; Oikawa, Azusa; Suzuki, Kiyofumi; Ogata, Atsushi; Friedrich, Michael W; Conrad, Ralf; Kamagata, Yoichi

2015-01-01

Reduction of crystalline Fe(III) oxides is one of the most important electron sinks for organic compound oxidation in natural environments. Yet the limited number of isolates makes it difficult to understand the physiology and ecological impact of the microorganisms involved. Here, two-stage cultivation was implemented to selectively enrich and isolate crystalline iron(III) oxide reducing microorganisms in soils and sediments. Firstly, iron reducers were enriched and other untargeted eutrophs were depleted by 2-years successive culture on a crystalline ferric iron oxide (i.e., goethite, lepidocrocite, hematite, or magnetite) as electron acceptor. Fifty-eight out of 136 incubation conditions allowed the continued existence of microorganisms as confirmed by PCR amplification. High-throughput Illumina sequencing and clone library analysis based on 16S rRNA genes revealed that the enrichment cultures on each of the ferric iron oxides contained bacteria belonging to the Deltaproteobacteria (mainly Geobacteraceae), followed by Firmicutes and Chloroflexi, which also comprised most of the operational taxonomic units (OTUs) identified. Venn diagrams indicated that the core OTUs enriched with all of the iron oxides were dominant in the Geobacteraceae while each type of iron oxides supplemented selectively enriched specific OTUs in the other phylogenetic groups. Secondly, 38 enrichment cultures including novel microorganisms were transferred to soluble-iron(III) containing media in order to stimulate the proliferation of the enriched iron reducers. Through extinction dilution-culture and single colony isolation, six strains within the Deltaproteobacteria were finally obtained; five strains belonged to the genus Geobacter and one strain to Pelobacter. The 16S rRNA genes of these isolates were 94.8-98.1% identical in sequence to cultured relatives. All the isolates were able to grow on acetate and ferric iron but their physiological characteristics differed considerably in terms of growth rate. Thus, the novel strategy allowed to enrich and isolate novel iron(III) reducers that were able to thrive by reducing crystalline ferric iron oxides.

Morphology, stability, and X-ray absorption spectroscopic study of iron oxide (Hematite) nanoparticles prepared by micelle nanolithography

NASA Astrophysics Data System (ADS)

Bera, Anupam; Bhattacharya, Atanu; Tiwari, N.; Jha, S. N.; Bhattacharyya, D.

2018-03-01

Currently, considerable effort is being made towards synthesis and characterization of iron oxide nanoparticles. In this article, we report on the preparation and characterization of iron oxide nanoparticle (NP) arrays supported on natively oxidized Si(100) surface. The NPs are synthesized by reverse micelle nanolithography technique and are then deposited onto natively oxidized Si(100) surface via spin-coating. Plasma oxidation followed by high temperature annealing results in a unimodal size distribution of pseudohexagonally-ordered array of iron oxide NPs (with ∼14 nm mean diameter and ∼5 nm mean height). High temperature annealing does not fragment the NPs. Particles are sinter-resistant: the unimodal arrays are robust with respect to thermal treatment. X-ray absorption spectroscopy (XAS), including X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), reveals that structure of the iron oxide particle resembles closely the hematite α-Fe2O3 structure. Furthermore, with the help of EXAFS spectra, we eliminate the possibility of γ-Fe2O3, Fe3O4, FeO and FeO(OH) structures for the NPs.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

The role of the iron catalyst in the toxicity of multi-walled carbon nanotubes (MWCNTs).

PubMed

Visalli, Giuseppa; Facciolà, Alessio; Iannazzo, Daniela; Piperno, Anna; Pistone, Alessandro; Di Pietro, Angela

2017-09-01

This study aimed to investigate the role of iron, used as a catalyst, in the biological response to pristine and functionalized multi-walled carbon nanotubes (p/fMWCNTs) with an iron content of 2.5-2.8%. Preliminarily, we assessed the pro-oxidant activity of MWCNTs-associated iron by an abiotic test. To evaluate iron bioavailability, we measured intracellular redox-active iron in A549 cells exposed to both MWCNT suspensions and to the cell medium preconditioned by MWCNTs, in order to assess the iron dissolution rate under physiological conditions. Moreover, in exposed cells, we detected ROS levels, 8-oxo-dG and mitochondrial function. The results clearly highlighted that MWCNTs- associated iron was not redox-active and that iron leakage did not occur under physiological conditions, including the oxidative burst of specialized cells. Despite this, in MWCNTs exposed cells, higher level of intracellular redox-active iron was measured in comparison to control and a significant time-dependent ROS increase was observed (P<0.01). Higher levels of 8-oxo-dG, a marker of oxidative DNA damage, and decreased mitochondrial function, confirmed the oxidative stress induced by MWCNTs. Based on the results we believe that oxidative damage could be attributable to the release of endogenous redox-active iron. This was due to the damage of acidic vacuolar compartment caused by endocytosis-mediated MWCNT internalization. Copyright © 2017 Elsevier GmbH. All rights reserved.

Gene identification and substrate regulation provide insights into sulfur accumulation during bioleaching with the psychrotolerant acidophile Acidithiobacillus ferrivorans.

PubMed

Liljeqvist, Maria; Rzhepishevska, Olena I; Dopson, Mark

2013-02-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments.

Gene Identification and Substrate Regulation Provide Insights into Sulfur Accumulation during Bioleaching with the Psychrotolerant Acidophile Acidithiobacillus ferrivorans

PubMed Central

Liljeqvist, Maria; Rzhepishevska, Olena I.

2013-01-01

The psychrotolerant acidophile Acidithiobacillus ferrivorans has been identified from cold environments and has been shown to use ferrous iron and inorganic sulfur compounds as its energy sources. A bioinformatic evaluation presented in this study suggested that Acidithiobacillus ferrivorans utilized a ferrous iron oxidation pathway similar to that of the related species Acidithiobacillus ferrooxidans. However, the inorganic sulfur oxidation pathway was less clear, since the Acidithiobacillus ferrivorans genome contained genes from both Acidithiobacillus ferrooxidans and Acidithiobacillus caldus encoding enzymes whose assigned functions are redundant. Transcriptional analysis revealed that the petA1 and petB1 genes (implicated in ferrous iron oxidation) were downregulated upon growth on the inorganic sulfur compound tetrathionate but were on average 10.5-fold upregulated in the presence of ferrous iron. In contrast, expression of cyoB1 (involved in inorganic sulfur compound oxidation) was decreased 6.6-fold upon growth on ferrous iron alone. Competition assays between ferrous iron and tetrathionate with Acidithiobacillus ferrivorans SS3 precultured on chalcopyrite mineral showed a preference for ferrous iron oxidation over tetrathionate oxidation. Also, pure and mixed cultures of psychrotolerant acidophiles were utilized for the bioleaching of metal sulfide minerals in stirred tank reactors at 5 and 25°C in order to investigate the fate of ferrous iron and inorganic sulfur compounds. Solid sulfur accumulated in bioleaching cultures growing on a chalcopyrite concentrate. Sulfur accumulation halted mineral solubilization, but sulfur was oxidized after metal release had ceased. The data indicated that ferrous iron was preferentially oxidized during growth on chalcopyrite, a finding with important implications for biomining in cold environments. PMID:23183980

Resistance to High-Temperature Oxidation and Wear of Various Ferrous Alloys Used in Rolling Mills

NASA Astrophysics Data System (ADS)

Delaunois, Fabienne; Stanciu, Victor Ioan; Sinnaeve, Mario

2018-03-01

Various materials are commonly used to manufacture work rolls for hot rolling mills, such as ICDP (Indefinite Chill Double Pour) cast irons, high-chromium white cast irons, and high speed steels (HSS). Various chemical compositions and microstructures are studied in order to optimize the in-use behavior of those grades of rolls. In this paper, six grades of ferrous alloys (an ICDP cast iron; an ICDP cast iron enriched in vanadium, niobium, and molybdenum; a HSS; a graphitic HSS; a high-chromium white cast iron (Hi-Cr); and a niobium-molybdenum-doped high-chromium white cast iron) were investigated. High-temperature oxidation tests with gravimetric means at 575 °C in water vapor atmosphere and sliding wear tests were carried out. The oxidation kinetics was followed during oxidation test. The microstructure was observed by optical and scanning electron microscopies. The oxides formed on the surface of the samples were analyzed by XRD and EDS. The thickness of the oxide scales and the mass gain were measured after oxidation test. The results showed that the behavior of all the grades differed. The oxide scale of HSS and HSS-G grades was fine and their friction coefficient was low. The weight gain after oxidation test of HSS was high. Hi-Cr and M-Hi-Cr grades presented highly porous oxide layer and an important increase of the friction coefficient during wear test. ICDP and M-ICDP had intermediate behavior.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

PubMed

Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

2012-11-30

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

ERIC Educational Resources Information Center

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2008-01-01

A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Zhang, Yijun; Liu, Ming; Peng, Bin; Zhou, Ziyao; Chen, Xing; Yang, Shu-Ming; Jiang, Zhuang-De; Zhang, Jie; Ren, Wei; Ye, Zuo-Guang

2016-01-01

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe2O3 and superparamagnetic Fe3O4 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe2O3 in a reducing atmosphere leads to the formation of the spinel Fe3O4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. The ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

Phosphate dynamics in an acidic mountain stream: Interactions involving algal uptake, sorption by iron oxide, and photoreduction

USGS Publications Warehouse

Tate, Cathy M.; Broshears, Robert E.; McKnight, Diane M.

1995-01-01

Acid mine drainage streams in the Rocky Mountains typically have few algal species and abundant iron oxide deposits which can sorb phosphate. An instream injection of radiolabeled phosphate (32P0,) into St. Kevin Gulch, an acid mine drainage stream, was used to test the ability of a dominant algal species, Ulothrix sp., to rapidly assimilate phosphate. Approximately 90% of the injected phosphate was removed from the water column in the 175-m stream reach. When shaded stream reaches were exposed to full sunlight after the injection ended, photoreductive dissolution of iron oxide released sorbed 32P, which was then also removed downstream. The removal from the stream was modeled as a first-order process by using a reactive solute transport transient storage model. Concentrations of 32P mass-’ of algae were typically lo-fold greater than concentrations in hydrous iron oxides. During the injection, concentrations of 32P increased in the cellular P pool containing soluble, low-molecular-weight compounds and confirmed direct algal uptake of 32P0, from water. Mass balance calculations indicated that algal uptake and sorption on iron oxides were significant in removing phosphate. We conclude that in stream ecosystems, PO, sorbed by iron oxides can act as a dynamic nutrient reservoir regulated by photoreduction.

First-principles calculations for XAS of infinite-layer iron oxides

NASA Astrophysics Data System (ADS)

Kodera, Mitsuru; Shishidou, Tatsuya; Oguchi, Tamio

2011-03-01

The oxygen defect perovskite SrFe O3 - x shows various properties such as the giant magnetoresistance effect and the thermoelectric effect. It had been believed that the oxygen content in SrFe O3 - x changes up to x = 0.5 . Recently, Tsujimoto et al . have succeeded in synthesizing the infinite-layer iron oxide SrFe O2 . SrFe O2 has a square-planar oxygen coordination, while the iron oxides usually have the tetrahedral and octahedral coordination. CaFe O2 has also infinite layer structure and the same magnetic ordering as SrFe O2 . However, it is suggested that the oxygen coordination of CaFe O2 is different from that of SrFe O2 . In order to investigate the electronic structure of iron in (Ca, Sr) Fe O2 , the x-ray absorption spectroscopy (XAS) spectrum has been measured. In this work, we perform the calculation for XAS spectrum near the Fe-K edge of (Ca, Sr) Fe O2 using the first-principles calculations. We compare the results with the experiment and discuss the electronic structure of iron in (Ca, Sr) Fe O2 .

Mineralized iron oxidizing bacteria from hydrothermal vents: targeting biosignatures on Mars

NASA Astrophysics Data System (ADS)

Leveille, R. J.

2010-12-01

Putative hydrothermal systems have been identified on Mars based on orbital imagery and rover-based analyses. Based on Earth analogs, hydrothermal systems on Mars would be highly attractive for their potential for preserving organic and inorganic biosignatures. For example, iron oxidizing bacteria are ubiquitous in marine and terrestrial hydrothermal systems, where they often display distinctive cell morphologies and are commonly encrusted by minerals, especially bacteriogenic iron oxides and silica. Microfossils of iron oxidizing bacteria have been found in ancient Si-Fe deposits and iron oxidation may be an ancient and widespread metabolic pathway. In order to investigate mineralized iron oxidizing bacteria as a biosignature, we have examined samples collected from extinct hydrothermal vents along Explorer Ridge, NE Pacific Ocean. In addition, microaerophilic iron oxidizing bacteria, isolated from active Pacific hydrothermal vents, were grown in a Fe-enriched seawater medium at constant pH (6.5) and O2 concentration (5%) in a controlled bioreactor system. Samples and experimental products were examined with a combination of variable-pressure and field-emission scanning electron microscopy (SEM), in some cases by preparing samples with a focused ion beam (FIB) milling system. Light-toned seafloor samples display abundant filamentous forms resembling, in both size and shape (1-5 microns in diameter and up to several microns in length), the twisted stalks of Gallionella and the elongated filaments of Leptothrix. Some samples consist entirely of low-density masses of silica (>90% Si) encrusted filamentous forms. The presence of unmineralized filamentous matter rich in C and Fe suggests that these are the remains of iron oxidizing bacteria. Mineralized filaments sectioned by FIB show variable internal material within semi-hollow, tubular-like features. Silica encrustations also show pseudo-concentric growth bands. In the bioreactor runs, abundant microbial growth and formation of an iron oxyhydroxide precipitate, either in direct association with the cells or within the growth medium, were observed. Preliminary analyses suggest that these precipitates are different from abiotic precipitates. Continuing work includes high-resolution TEM observations of cultured organisms and biogenic iron minerals, Raman and reflectance spectroscopy of precipitates, examination of seafloor incubation experiments, and bioreactor silicification experiments in order to better understand the Fe-Si fossilization process. Microaerophilic iron oxidation could have existed on the early Earth in environments containing small amounts of oxygen produced either by locally-concentrated photosynthetic microorganisms (e.g., cyanobacteria) or by chemical reactions. By analogy, similar subsurface or near-surface microaerophilic environments could have existed on Mars in the past, including in low-temperature hydrothermal systems. The distinctive morphologies and Fe-Si mineralization patterns of iron oxidizing bacteria could be a useful biosignature to search for on Mars. Deposits and features similar to those described here could be identified on Mars with existing technologies, and thus hydrothermal systems represent an attractive target for future surface and sample return missions.

Fossilization of Iron-Oxidizing Bacteria at Hydrothermal Vents: a Useful Biosignature on Mars?

NASA Astrophysics Data System (ADS)

Leveille, R. J.; Lui, S.

2009-05-01

Iron oxidizing bacteria are ubiquitous in marine and terrestrial environments on Earth, where they often display distinctive cell morphologies and are commonly encrusted by minerals, especially bacteriogenic iron oxides and silica. Putative microfossils of iron oxidizing bacteria have been found in jaspers as old as 490Ma and microbial iron oxidation may be an ancient metabolic pathway. In order to investigate the usefulness of mineralized iron oxidizing bacteria as a biosignature, we have examined mineral samples collected from relict hydrothermal systems along Explorer Ridge, NE Pacific Ocean. In addition, microaerophilic, neutrophilic iron oxidizing bacteria, isolated from Pacific hydrothermal vents, were grown in a Fe-enriched seawater medium at constant pH (6.5) and oxygen concentration (5 percent) in a controlled bioreactor system. Both natural samples and experimental products were examined with a combination of variable pressure scanning electron microscopy (SEM), field emission gun SEM, and in some cases by preparing samples with a focused ion beam (FIB) milling system. Natural seafloor samples display abundant filamentous forms often resembling, in both size and shape, the twisted stalks of Gallionella and the elongated filaments of Leptothrix. Generally, these filamentous features are 1-5 microns in diameter and up to several microns in length. Some samples consist entirely of low- density, porous masses of silica encrusted filamentous forms. Presumably, these masses were formed by a rapid precipitation by the influx of silica-rich fluids into a microbial mat dominated by bacteria with filamentous morphologies. The presence of rare, amorphous (unmineralized) filamentous matter rich in C and Fe suggests that these bacteria were iron oxidizers. There is no evidence that sulfur oxidizers were present. Filamentous features sectioned by FIB milling show internal material within semi-hollow tubular-like features. Silica encrustations also show pseudo-concentric growth bands. In the bioreactor cultures, constant conditions led to abundant microbial growth and formation of an iron oxyhydroxide precipitate, either in direct association with the cells or within the growth medium. This suggests that not all of the iron precipitation is biogenic in origin. Cells typically show a filamentous morphology reminiscent of the mineral-encrusted forms observed in the natural samples. Continuing work includes high-resolution TEM observations of cultured organisms, examination of 2-year long in situ seafloor incubation experiments, and bioreactor silicification experiments in order to better understand the roles of iron and silica in the fossilization process. Microaerophilic iron oxidation could have existed on the early Earth in environments containing small amounts of oxygen produced either by locally concentrated photosynthetic microorganisms (e.g., cyanobacteria) or abiotically, as proposed for the subsurface of the Fe-dominated Rio Tinto (Spain) basin system. By analogy, similar subsurface or near-surface microaerophilic environments could have existed on Mars in the past. The distinctive morphologies and mineralization patterns of iron oxidizing bacteria could be a useful biosignature to search for on Mars. Deposits and biogenic features similar to those described here could theoretically be identified on Mars with existing imaging and analytical technologies. Therefore, future missions to Mars should target ancient hydrothermal systems, some of which have been putatively identified already.

X-Ray Photoelectron Spectroscopic Characterization of Iron Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Radu, T.; Iacovita, C.; Benea, D.; Turcu, R.

2017-05-01

We report X-ray photoelectron spectroscopy (XPS) results on iron oxide magnetic nanoparticle (Fe3O4) synthesized using solvothermal reduction in the presence of polyethylene glycol. The magnetite obtained was employed as precursor for the synthesis of γ-Fe2O3 (by oxygen dissociation) which in turn was transformed into α-Fe2O3. We confirmed the magnetite, maghemite and hematite structure by Fourier Transformed Spectroscopy (FTIR) and X-ray diffraction (XRD). The analysis of the XPS core level and valence band (VB) photoemission spectra for all investigated samples is discussed in terms of the degree of iron oxidation. This is of fundamental importance to better understand the electronic structure of the obtained iron oxide nanoparticles in order to control and improve their quality for specific biomedical applications. Moreover, theoretical band structure calculations are performed for magnetite and the separate contributions of Fe in tetragonal and octahedral environment are shown.

Laboratory Investigation of Complex Conductivity and Magnetic Susceptibility on Natural Iron Oxide Coated Sand

NASA Astrophysics Data System (ADS)

Wang, C.; Slater, L. D.; Day-Lewis, F. D.; Briggs, M. A.

2017-12-01

Redox reactions occurring at the oxic/anoxic interface where groundwater discharges to surface water commonly result in iron oxide deposition that coats sediment grains. With relatively large total surface area, these iron oxide coated sediments serve as a sink for sorption of dissolved contaminants, although this sink may be temporary if redox conditions fluctuate with varied flow conditions. Characterization of the distribution of iron oxides in streambed sediments could provide valuable understanding of biogeochemical reactions and the ability of a natural system to sorb contaminants. Towards developing a field methodology, we conducted laboratory spectral induced polarization (SIP) and magnetic susceptibility (MS) measurements on natural iron oxide coated sand (Fe-sand) with grain sizes ranging from 0.3 to 2.0 mm in order to assess the sensitivity of these measurements to iron oxides in sediments. The Fe-sand was also sorted by sieving into various grain sizes to study the impact of grain size on the polarization mechanisms. The unsorted Fe-sand saturated with 0.01 S/m NaCl solution exhibited a distinct phase response ( > 4 mrad) in the frequency range from 0.001 to 100 Hz whereas regular silica sand was characterized by a phase response less than 1 mrad under the same conditions. The presence of iron oxide substantially increased MS (3.08×10-3 SI) over that of regular sand ( < 10-5 SI). An increase of both phase peak and relaxation time was found with increasing grain size of the sorted Fe-sand. Laboratory results demonstrated that SIP and MS may be well suited to mapping the distribution of iron oxides in streambed sediments associated with anoxic groundwater discharge.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

Bacterial oxidation of ferrous iron at low temperatures.

PubMed

Kupka, Daniel; Rzhepishevska, Olena I; Dopson, Mark; Lindström, E Börje; Karnachuk, Olia V; Tuovinen, Olli H

2007-08-15

This study comprises the first report of ferrous iron oxidation by psychrotolerant, acidophilic iron-oxidizing bacteria capable of growing at 5 degrees C. Samples of mine drainage-impacted surface soils and sediments from the Norilsk mining region (Taimyr, Siberia) and Kristineberg (Skellefte district, Sweden) were inoculated into acidic ferrous sulfate media and incubated at 5 degrees C. Iron oxidation was preceded by an approximately 3-month lag period that was reduced in subsequent cultures. Three enrichment cultures were chosen for further work and one culture designated as isolate SS3 was purified by colony isolation from a Norilsk enrichment culture for determining the kinetics of iron oxidation. The 16S rRNA based phylogeny of SS3 and two other psychrotolerant cultures, SS5 from Norilsk and SK5 from Northern Sweden, was determined. Comparative analysis of amplified 16S rRNA gene sequences showed that the psychrotolerant cultures aligned within Acidithiobacillus ferrooxidans. The rate constant of iron oxidation by growing cultures of SS3 was in the range of 0.0162-0.0104 h(-1) depending on the initial pH. The oxidation kinetics followed an exponential pattern, consistent with a first order rate expression. Parallel iron oxidation by a mesophilic reference culture of Acidithiobacillus ferrooxidans was extremely slow and linear. Precipitates harvested from the 5 degrees C culture were identified by X-ray diffraction as mixtures of schwertmannite (ideal formula Fe(8)O(8)(OH)(6)SO(4)) and jarosite (KFe(3)(SO(4))(2)(OH)(6)). Jarosite was much more dominant in precipitates produced at 30 degrees C. (c) 2007 Wiley Periodicals, Inc.

Intracellular trafficking of silicon particles and logic-embedded vectors

NASA Astrophysics Data System (ADS)

Ferrati, Silvia; Mack, Aaron; Chiappini, Ciro; Liu, Xuewu; Bean, Andrew J.; Ferrari, Mauro; Serda, Rita E.

2010-08-01

Mesoporous silicon particles show great promise for use in drug delivery and imaging applications as carriers for second-stage nanoparticles and higher order particles or therapeutics. Modulation of particle geometry, surface chemistry, and porosity allows silicon particles to be optimized for specific applications such as vascular targeting and avoidance of biological barriers commonly found between the site of drug injection and the final destination. In this study, the intracellular trafficking of unloaded carrier silicon particles and carrier particles loaded with secondary iron oxide nanoparticles was investigated. Following cellular uptake, membrane-encapsulated silicon particles migrated to the perinuclear region of the cell by a microtubule-driven mechanism. Surface charge, shape (spherical and hemispherical) and size (1.6 and 3.2 μm) of the particle did not alter the rate of migration. Maturation of the phagosome was associated with an increase in acidity and acquisition of markers of late endosomes and lysosomes. Cellular uptake of iron oxide nanoparticle-loaded silicon particles resulted in sorting of the particles and trafficking to unique destinations. The silicon carriers remained localized in phagosomes, while the second stage iron oxide nanoparticles were sorted into multi-vesicular bodies that dissociated from the phagosome into novel membrane-bound compartments. Release of iron from the cells may represent exocytosis of iron oxide nanoparticle-loaded vesicles. These results reinforce the concept of multi-functional nanocarriers, in which different particles are able to perform specific tasks, in order to deliver single- or multi-component payloads to specific sub-cellular compartments.Mesoporous silicon particles show great promise for use in drug delivery and imaging applications as carriers for second-stage nanoparticles and higher order particles or therapeutics. Modulation of particle geometry, surface chemistry, and porosity allows silicon particles to be optimized for specific applications such as vascular targeting and avoidance of biological barriers commonly found between the site of drug injection and the final destination. In this study, the intracellular trafficking of unloaded carrier silicon particles and carrier particles loaded with secondary iron oxide nanoparticles was investigated. Following cellular uptake, membrane-encapsulated silicon particles migrated to the perinuclear region of the cell by a microtubule-driven mechanism. Surface charge, shape (spherical and hemispherical) and size (1.6 and 3.2 μm) of the particle did not alter the rate of migration. Maturation of the phagosome was associated with an increase in acidity and acquisition of markers of late endosomes and lysosomes. Cellular uptake of iron oxide nanoparticle-loaded silicon particles resulted in sorting of the particles and trafficking to unique destinations. The silicon carriers remained localized in phagosomes, while the second stage iron oxide nanoparticles were sorted into multi-vesicular bodies that dissociated from the phagosome into novel membrane-bound compartments. Release of iron from the cells may represent exocytosis of iron oxide nanoparticle-loaded vesicles. These results reinforce the concept of multi-functional nanocarriers, in which different particles are able to perform specific tasks, in order to deliver single- or multi-component payloads to specific sub-cellular compartments. Electronic supplementary information (ESI) available: Confocal microscopy image showing internalized negative particles, and movie of the intracellular migration of silicon particles. See DOI: 10.1039/c0nr00227e

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

The aerobic respiratory chain of the acidophilic archaeon Ferroplasma acidiphilum: A membrane-bound complex oxidizing ferrous iron.

PubMed

Castelle, Cindy J; Roger, Magali; Bauzan, Marielle; Brugna, Myriam; Lignon, Sabrina; Nimtz, Manfred; Golyshina, Olga V; Giudici-Orticoni, Marie-Thérèse; Guiral, Marianne

2015-08-01

The extremely acidophilic archaeon Ferroplasma acidiphilum is found in iron-rich biomining environments and is an important micro-organism in naturally occurring microbial communities in acid mine drainage. F. acidiphilum is an iron oxidizer that belongs to the order Thermoplasmatales (Euryarchaeota), which harbors the most extremely acidophilic micro-organisms known so far. At present, little is known about the nature or the structural and functional organization of the proteins in F. acidiphilum that impact the iron biogeochemical cycle. We combine here biochemical and biophysical techniques such as enzyme purification, activity measurements, proteomics and spectroscopy to characterize the iron oxidation pathway(s) in F. acidiphilum. We isolated two respiratory membrane protein complexes: a 850 kDa complex containing an aa3-type cytochrome oxidase and a blue copper protein, which directly oxidizes ferrous iron and reduces molecular oxygen, and a 150 kDa cytochrome ba complex likely composed of a di-heme cytochrome and a Rieske protein. We tentatively propose that both of these complexes are involved in iron oxidation respiratory chains, functioning in the so-called uphill and downhill electron flow pathways, consistent with autotrophic life. The cytochrome ba complex could possibly play a role in regenerating reducing equivalents by a reverse ('uphill') electron flow. This study constitutes the first detailed biochemical investigation of the metalloproteins that are potentially directly involved in iron-mediated energy conservation in a member of the acidophilic archaea of the genus Ferroplasma. Copyright © 2015 Elsevier B.V. All rights reserved.

Inclusion compounds between α-, β- and γ-cyclodextrins: iron II lactate: a theoretical and experimental study using diffusion coefficients and molecular mechanics

NASA Astrophysics Data System (ADS)

Leite, Rosiley A.; Lino, Antonio C. S.; Takahata, Yuji

2003-01-01

The inclusion compounds between iron II lactate and three different cyclodextrins (CDs) were studied by means of experimental and theoretical data. The importance of iron II in the human metabolism effort the necessity of a minimum concentration to the human life. Malnutrition is one great problem in social politics of many countries on the world. The possibility to the development of novel medicines with the iron II species stable look for an increase on the efficiency for this kind of aid. Kinetics measurements confirm the possibility to stop the oxidation reaction. It was the first indication of efficient molecular encapsulation. Diffusion coefficient measurements were carried out by Taylor-Aris diffusion technique. The decrease of diffusion coefficients measured for iron II lactate when alone and forming the inclusion complexes was obtained for all hosts molecules used. Molecular Mechanics calculations were performed to elucidate the perfect arrange of iron II lactate inside CDs cavity. No great differences were obtained to the binding energy for the different hosts. Using the software HyperChem6.03v MM+, AMBER94 and OPLS Forced Fields for iron atom in two chemical environments (a) vacuum and (b) with addition of 250 water molecules (MM+). The solvent treatment was decisive to the order of stability. This order was β-CD>γ-CD>α-CD, the same order of solubility in water. The results contained in this work confirm the possibility to protect iron II lactate against oxidation.

Ligand-hole localization in oxides with unusual valence Fe

PubMed Central

Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

2012-01-01

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

DOE PAGES

Zhang, Yijun; Liu, Ming; Peng, Bin; ...

2016-01-27

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe 2O 3 and superparamagnetic Fe 2O 3with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe 2O 3 in a reducing atmosphere leads to the formation of the spinel Fe 3O 4 phase which displaysmore » a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.« less

Application of Response Surface Methodology on Leaching of Iron from Partially Laterised Khondalite Rocks: A Bauxite Mining Waste

NASA Astrophysics Data System (ADS)

Swain, Ranjita; Bhima Rao, R.

2018-04-01

In the present investigation, response surface methodology (RSM) is used for a quadratic model that continuously controls the process parameters. This model is used to optimize the removal of iron oxide from Partially Laterised Khondalite (PLK) rocks which is influenced by several independent variables namely acid concentration, time and temperature. Second order response functions are produced for leaching of iron oxide from PLK rocks-a bauxite mining waste. In RSM, Box-Behnken design is used for the process optimization to achieve maximum removal of iron oxide. The influence of the process variables of leaching of iron oxide is presented in the form of 3-D response graphs. The results of this investigation reveals that 3 M hydrochloric acid concentration, 240 min time and 373 K temperature are found to be the best conditions for removal of 99% Fe2O3. The product obtain at this condition contain 80% brightness which is suitable for ceramic and filler industry applications. The novelity of the work is that the waste can be a value added product after suitable physical beneficiation and chemical treatment.

Characterisation and Processing of Some Iron Ores of India

NASA Astrophysics Data System (ADS)

Krishna, S. J. G.; Patil, M. R.; Rudrappa, C.; Kumar, S. P.; Ravi, B. P.

2013-10-01

Lack of process characterization data of the ores based on the granulometry, texture, mineralogy, physical, chemical, properties, merits and limitations of process, market and local conditions may mislead the mineral processing entrepreneur. The proper implementation of process characterization and geotechnical map data will result in optimized sustainable utilization of resource by processing. A few case studies of process characterization of some Indian iron ores are dealt with. The tentative ascending order of process refractoriness of iron ores is massive hematite/magnetite < marine black iron oxide sands < laminated soft friable siliceous ore fines < massive banded magnetite quartzite < laminated soft friable clayey aluminous ore fines < massive banded hematite quartzite/jasper < massive clayey hydrated iron oxide ore < manganese bearing iron ores massive < Ti-V bearing magnetite magmatic ore < ferruginous cherty quartzite. Based on diagnostic process characterization, the ores have been classified and generic process have been adopted for some Indian iron ores.

Exploring Microbial Iron Oxidation in Wetland Soils

NASA Astrophysics Data System (ADS)

Wang, J.; Muyzer, G.; Bodelier, P. L. E.; den Oudsten, F.; Laanbroek, H. J.

2009-04-01

Iron is one of the most abundant elements on earth and is essential for life. Because of its importance, iron cycling and its interaction with other chemical and microbial processes has been the focus of many studies. Iron-oxidizing bacteria (FeOB) have been detected in a wide variety of environments. Among those is the rhizosphere of wetland plants roots which release oxygen into the soil creating suboxic conditions required by these organisms. It has been reported that in these rhizosphere microbial iron oxidation proceeds up to four orders of magnitude faster than strictly abiotic oxidation. On the roots of these wetland plants iron plaques are formed by microbial iron oxidation which are involved in the sequestering of heavy metals as well organic pollutants, which of great environmental significance.Despite their important role being catalysts of iron-cycling in wetland environments, little is known about the diversity and distribution of iron-oxidizing bacteria in various environments. This study aimed at developing a PCR-DGGE assay enabling the detection of iron oxidizers in wetland habitats. Gradient tubes were used to enrich iron-oxidizing bacteria. From these enrichments, a clone library was established based on the almost complete 16s rRNA gene using the universal bacterial primers 27f and 1492r. This clone library consisted of mainly α- and β-Proteobacteria, among which two major clusters were closely related to Gallionella spp. Specific probes and primers were developed on the basis of this 16S rRNA gene clone library. The newly designed Gallionella-specific 16S rRNA gene primer set 122f/998r was applied to community DNA obtained from three contrasting wetland environments, and the PCR products were used in denaturing gradient gel electrophoresis (DGGE) analysis. A second 16S rRNA gene clone library was constructed using the PCR products from one of our sampling sites amplified with the newly developed primer set 122f/998r. The cloned 16S rRNA gene sequences all represented novel culturable iron oxidizers most closely related to Gallionella spp. Based on their nucleotide sequences four groups could be identified, which were comparable to the DGGE banding pattern obtained before with the gradient tubes enrichments. The above mentioned nested PCR-DGGE method was used to study the distribution and community composition of Gallionella-like iron-oxidizing bacteria under the influence of plants species, soil depth, as well as season. Soil samples from Appels, Belgium, an intertidal, freshwater marsh known to hold intensive iron cycling, were taken from 5 different vegetation types in April, July and October 2007. Soil cores were sliced at 1-cm intervals and subjected to chemical and molecular analyses. The DGGE patterns showed that the community of iron-oxidizing bacteria differed with vegetation type, and sediment depth. Samples taken in autumn held lower diversity in Gallionella-related iron oxidizers than those sampled in spring and summer.

Efficient Low-pH Iron Removal by a Microbial Iron Oxide Mound Ecosystem at Scalp Level Run.

PubMed

Grettenberger, Christen L; Pearce, Alexandra R; Bibby, Kyle J; Jones, Daniel S; Burgos, William D; Macalady, Jennifer L

2017-04-01

Acid mine drainage (AMD) is a major environmental problem affecting tens of thousands of kilometers of waterways worldwide. Passive bioremediation of AMD relies on microbial communities to oxidize and remove iron from the system; however, iron oxidation rates in AMD environments are highly variable among sites. At Scalp Level Run (Cambria County, PA), first-order iron oxidation rates are 10 times greater than at other coal-associated iron mounds in the Appalachians. We examined the bacterial community at Scalp Level Run to determine whether a unique community is responsible for the rapid iron oxidation rate. Despite strong geochemical gradients, including a >10-fold change in the concentration of ferrous iron from 57.3 mg/liter at the emergence to 2.5 mg/liter at the base of the coal tailings pile, the bacterial community composition was nearly constant with distance from the spring outflow. Scalp Level Run contains many of the same taxa present in other AMD sites, but the community is dominated by two strains of Ferrovum myxofaciens , a species that is associated with high rates of Fe(II) oxidation in laboratory studies. IMPORTANCE Acid mine drainage pollutes more than 19,300 km of rivers and streams and 72,000 ha of lakes worldwide. Remediation is frequently ineffective and costly, upwards of $100 billion globally and nearly $5 billion in Pennsylvania alone. Microbial Fe(II) oxidation is more efficient than abiotic Fe(II) oxidation at low pH (P. C. Singer and W. Stumm, Science 167:1121-1123, 1970, https://doi.org/10.1126/science.167.3921.1121). Therefore, AMD bioremediation could harness microbial Fe(II) oxidation to fuel more-cost-effective treatments. Advances will require a deeper understanding of the ecology of Fe(II)-oxidizing microbial communities and the factors that control their distribution and rates of Fe(II) oxidation. We investigated bacterial communities that inhabit an AMD site with rapid Fe(II) oxidation and found that they were dominated by two operational taxonomic units (OTUs) of Ferrovum myxofaciens , a taxon associated with high laboratory rates of iron oxidation. This research represents a step forward in identifying taxa that can be used to enhance cost-effective AMD bioremediation. Copyright © 2017 American Society for Microbiology.

Intracellular Trafficking of Silicon Particles and Logic-Embedded Vectors

PubMed Central

Ferrati, Silvia; Mack, Aaron; Chiappini, Ciro; Liu, Xuewu; Bean, Andrew J.; Ferrari, Mauro; Serda, Rita E.

2010-01-01

Mesoporous silicon particles show great promise for use in drug delivery and imaging applications as carriers for second-stage nanoparticles and higher order particles or therapeutics. Modulation of particle geometry, surface chemistry, and porosity allows silicon particles to be optimized for specific applications such as vascular targeting and avoidance of biological barriers commonly found between the site of drug injection and the final destination. In this study, the intracellular trafficking of unloaded carrier silicon particles and carrier particles loaded with secondary iron oxide nanoparticles was investigated. Following cellular uptake, membrane-encapsulated silicon particles migrated to the perinuclear region of the cell by a microtubule-driven mechanism. Surface charge, shape (spherical and hemispherical) and size (1.6 and 3.2 μm) of the particle did not alter the rate of migration. Maturation of the phagosome was associated with an increase in acidity and acquisition of markers of late endosomes and lysosomes. Cellular uptake of iron oxide nanoparticle-loaded silicon particles resulted in sorting of the particles and trafficking to unique destinations. The silicon carriers remained localized in phagosomes, while the second stage iron oxide nanoparticles were sorted into multi-vesicular bodies that dissociated from the phagosome into novel membrane-bound compartments. Release of iron from the cells may represent exocytosis of iron oxide nanoparticle-loaded vesicles. These results reinforce the concept of multi-functional nanocarriers, in which different particles are able to perform specific tasks, in order to deliver single- or multi-component payloads to specific sub-cellular compartments. PMID:20820744

An empirical approach to predicting long term behavior of metal particle based recording media

NASA Technical Reports Server (NTRS)

Hadad, Allan S.

1991-01-01

Alpha iron particles used for magnetic recording are prepared through a series of dehydration and reduction steps of alpha-Fe2O3-H2O resulting in acicular, polycrystalline, body centered cubic (bcc) alpha-Fe particles that are single magnetic domains. Since fine iron particles are pyrophoric by nature, stabilization processes had to be developed in order for iron particles to be considered as a viable recording medium for long term archival (i.e., 25+ years) information storage. The primary means of establishing stability is through passivation or controlled oxidation of the iron particle's surface. Since iron particles used for magnetic recording are small, additional oxidation has a direct impact on performance especially where archival storage of recorded information for long periods of time is important. Further stabilization chemistry/processes had to be developed to guarantee that iron particles could be considered as a viable long term recording medium. In an effort to retard the diffusion of iron ions through the oxide layer, other elements such as silicon, aluminum, and chromium have been added to the base iron to promote more dense scale formation or to alleviate some of the non-stoichiometric behavior of the oxide or both. The presence of water vapor has been shown to disrupt the passive layer, subsequently increasing the oxidation rate of the iron. A study was undertaken to examine the degradation in magnetic properties as a function of both temperature and humidity on silicon-containing iron particles between 50-120 deg C and 3-89 percent relative humidity. The methodology to which experimental data was collected and analyzed leading to predictive capability is discussed.

On the synthesis and magnetic properties of multiwall carbon nanotube-superparamagnetic iron oxide nanoparticle nanocomposites.

PubMed

Narayanan, T N; Mary, A P Reena; Shaijumon, M M; Ci, Lijie; Ajayan, P M; Anantharaman, M R

2009-02-04

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT-SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at approximately 110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT-SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT-SPION composite can be envisaged as a good agent for various biomedical applications.

Differential proteomics analysis of the surface heterogeneity of dextran iron oxide nanoparticles and the implications for their in vivo clearance

PubMed Central

Simberg, Dmitri; Park, Ji-Ho; Karmali, Priya P.; Zhang, Wan-Ming; Merkulov, Sergei; McCrae, Keith; Bhatia, Sangeeta; Sailor, Michael; Ruoslahti, Erkki

2009-01-01

In order to understand the role of plasma proteins in the rapid liver clearance of dextran-coated superparamagnetic iron oxide (SPIO) in vivo, we analyzed the full repertoire of SPIO-binding blood proteins using novel two-dimensional differential mass spectrometry approach. The identified proteins showed specificity for surface domains of the nanoparticles: mannan-binding lectins bound to the dextran coating, histidine-rich glycoprotein and kininogen bound to the iron oxide part, and the complement lectin and contact clotting factors were secondary binders. Nanoparticle clearance studies in knockout mice suggested that these proteins, as well as several previously identified opsonins, do not play a significant role in the SPIO clearance. However, both the dextran coat and the iron oxide core remained accessible to specific probes after incubation of SPIO in plasma, suggesting that the nanoparticle surface could be available for recognition by macrophages, regardless of protein coating. These data provide guidance to rational design of bioinert, long-circulating nanoparticles. PMID:19394687

Differential proteomics analysis of the surface heterogeneity of dextran iron oxide nanoparticles and the implications for their in vivo clearance.

PubMed

Simberg, Dmitri; Park, Ji-Ho; Karmali, Priya P; Zhang, Wan-Ming; Merkulov, Sergei; McCrae, Keith; Bhatia, Sangeeta N; Sailor, Michael; Ruoslahti, Erkki

2009-08-01

In order to understand the role of plasma proteins in the rapid liver clearance of dextran-coated superparamagnetic iron oxide (SPIO) in vivo, we analyzed the full repertoire of SPIO-binding blood proteins using novel two-dimensional differential mass spectrometry approach. The identified proteins showed specificity for surface domains of the nanoparticles: mannan-binding lectins bound to the dextran coating, histidine-rich glycoprotein and kininogen bound to the iron oxide part, and the complement lectin and contact clotting factors were secondary binders. Nanoparticle clearance studies in knockout mice suggested that these proteins, as well as several previously identified opsonins, do not play a significant role in the SPIO clearance. However, both the dextran coat and the iron oxide core remained accessible to specific probes after incubation of SPIO in plasma, suggesting that the nanoparticle surface could be available for recognition by macrophages, regardless of protein coating. These data provide guidance to rational design of bioinert, long-circulating nanoparticles.

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

NASA Astrophysics Data System (ADS)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

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.

High Resolution Transmission Electron Microscopy (HRTEM) of nanophase ferric oxides

NASA Technical Reports Server (NTRS)

Golden, D. C.; Morris, R. V.; Ming, D. W.; Lauer, H. V., Jr.

1994-01-01

Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).

Amphorous hydrated Fe(III) sulfate: metastable product and bio-geochemical marker of iron oxidizing thiobacilli

NASA Astrophysics Data System (ADS)

Lazaroff, Norman; Jollie, John; Dugan, Patrick R.

1998-07-01

Chemolithotrophic iron oxidation by Thiobacillus ferrooxidans and other iron oxidizing thiobacilli produce an Fe(III) sulfato complex that polymerizes as x-ray amorphous filaments approximately 40 nm in diameter. The precursor complex in solutionis seen by ATR-FTIR spectroscopy to have a sulfate spectrum resembling the v(subscript 3) and v(subscript 1) vibrational modes of the precipitated polymer. Chemically similar precipitates prepared by oxidation of acid ferrous sulfate with hydrogen peroxide have a different micromorphology, higher iron/sulfur ratio and acid solubility than the bacterial product. They possess coalescing globular microstructures composed of compacted micro-fibrils. Scanning electron microscopy and diffuse reflectance FTIR show the formation of iron polymer on the surface of immobilized cells of T. ferrooxidans, oxidizing iron during the corrosion of steel. Although spatially separated form the steel coupons by a membrane filter, the cell walls become covered with tufts of amorphous hydrated Fe(III) sulfate. The metastable polymer is converted to crystalline goethite, lepidocrocite, and magnetite in that order, as the pH rises due to proton reduction at cathodic sites on the steel. The instability of the iron polymer to changes in pH is also evidenced by the loss of sulfate when washed with lithium hydroxide solution at pH 8. Under those conditions there is little change in micromorphology, but restoration of sulfate with sulfuric acid at pH 2.5, fails to re-establish the original chemical structure. Adding sulfate salts of appropriate cations to solutions of the Fe(III) sulfato complex or suspensions of its precipitated polymer in dilute sulfuric acid, result in dissociation of the metastable complex followed by crystallization of ferric ions and sulfate in jarosites. Jarosites and other derivatives of iron precipitation by iron oxidizing thiobacilli, form conspicuous deposits in areas of natural pyrite leaching. The role of iron oxidizing thiobacilli in pyrite leaching, biohydrometallurgy, acid mine drainage, and the cycle of iron and sulfur in nature, has been studied for nearly 50 years. The manifestation of those activities, so widespread on Earth, can be a clue for seeking evidence of life elsewhere.

Insights into the toxicity of iron oxides nanoparticles in land snails.

PubMed

Sidiropoulou, Eirini; Feidantsis, Konstantinos; Kalogiannis, Stavros; Gallios, George P; Kastrinaki, Georgia; Papaioannou, Eleni; Václavíková, Miroslava; Kaloyianni, Martha

2018-04-01

The use of manufactured nanoparticles (NPs) is spreading rapidly across technology and medicine fields, posing concerns about their consequence on ecosystems and human health. The present study aims to assess the biological responses triggered by iron oxide NPs (IONPs) and iron oxide NPs incorporated into zeolite (IONPZ) in relation to oxidative stress on the land snail Helix aspersa in order to investigate its use as a biomarker for terrestrial environments. Morphology and structure of both NPs were characterized. Snail food was supplemented with a range of concentrations of IONPs and IONPZ and values of the hemocyte lysosomal membranes' destabilization by 50% were estimated by the neutral red retention (NRRT50) assay. Subsequently, snails were fed with NPs concentrations equal to half of the NRRT50 values, 0.05 mg L -1 for IONPs and 1 mg L -1 for IONPZ, for 1, 5, 10 and 20 days. Both effectors induced oxidative stress in snails' hemocytes compared to untreated animals. The latter was detected by NRRT changes, reactive oxygen species (ROS) production, lipid peroxidation estimation, DNA integrity loss, measurement of protein carbonyl content by an enzyme-linked immunoabsorbent assay (ELISA), determination of ubiquitin conjugates and cleaved caspases conjugates levels. The results showed that the simultaneous use of the parameters tested could constitute possible reliable biomarkers for the evaluation of NPs toxicity. However, more research is required in order to enlighten the disposal and toxic impact of iron oxide NPs on the environment to ensure their safe use in the future. Copyright © 2018 Elsevier Inc. All rights reserved.

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

PubMed Central

Bobek, Michael M.; Stehle, Richard C.; Hahn, David W.

2012-01-01

A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM) and electron dispersive X-ray spectroscopy (EDS), the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

Adsorption of phthalic acid and salicylic acid and their effect on exchangeable Al capacity of variable-charge soils.

PubMed

Li, Jiuyu; Xu, Renkou

2007-02-01

Low-molecular-weight (LMW) organic acids may be adsorbed by soils and the adsorption could affect their biodegradation and efficiency in many soil processes. In the present study, the adsorption of phthalic acid and salicylic acid and their effect on the exchangeable Al capacity of variable-charge soils were investigated. The results indicated that phthalic acid and salicylic acid were adsorbed by four variable-charge soils to some extent, oxisols showed a greater adsorption capacity for organic acids than ultisols, and the ability of the four variable-charge soils to adsorb the organic acids at different pH generally followed the order Kunming oxisol > Xuwen oxisol > Jinxian ultisol > Lechang ultisol, which was closely related to their content of free iron oxides and amorphous iron and aluminum oxides. The adsorption of organic acids induced a decrease in the zeta potentials of soils and oxides. Goethite has greater adsorption capacity for organic acid than Xuwen oxisol and the adsorption of organic acids resulted in a bigger decrease in the zeta potential of goethite suspensions. After free iron oxides were removed, less organic acid was adsorbed by Xuwen oxisol and no change was observed in zeta potential for the soil suspension after organic acid was added. The presence of phthalic acid increased the capacity of exchangeable Al and the increment in the four variable-charge soils also followed the order Kunming oxisol > Xuwen oxisol > Lechang ultisol and Jinxian ultisol. The presence of salicylic acid increased the capacity of exchangeable Al in Kunming oxisol, Xuwen oxisol, and Jinxian ultisol, but decreased it in Lechang ultisol due to less adsorption of the acid and formation of soluble Al-salicylate complexes in solution. After free iron oxides were removed, less effect of organic acid on exchangeable Al was observed for Xuwen oxisol, which further confirmed that the iron oxides played a significant role in organic acid adsorption and had a consequent effect on the capacity of exchangeable Al in variable-charge soils. Therefore, the higher the content of iron oxides, the greater the adsorption of organic acids by soils and the greater the increase in soil exchangeable Al induced by the organic acids.

Biodistribution of newly synthesized PHEA-based polymer-coated SPION in Sprague Dawley rats as magnetic resonance contrast agent

PubMed Central

Park, Junsung; Cho, Wonkyung; Park, Hee Jun; Cha, Kwang-Ho; Ha, Dae-Chul; Choi, Youn-Woong; Lee, Ha-Young; Cho, Sun-Hang; Hwang, Sung-Joo

2013-01-01

Objectives The purpose of this study was to observe the pharmacokinetic behavior of newly synthesized biocompatible polymers based on polyhydroxyethylaspartamide (PHEA) to be used to coat an iron oxide core to make superparamagnetic iron oxide nanoparticles (SPION). Materials and methods The isotopes [14C] and [59Fe] were used to label the polymer backbone (CLS) and iron oxide core (FLS), respectively. In addition, unradiolabeled cold superparamagnetic iron oxide nanoparticles (SPION/ULS) were synthesized to characterize particle size by dynamic light scattering, morphology by transmission electron microscopy, and in vivo magnetic resonance imaging (MRI). CLS and FLS were used separately to investigate the behavior of both the synthesized polymer and [Fe] in Sprague Dawley (SD) rats, respectively. Because radioactivity of the isotopes was different by β for CLS and γ for FLS, synthesis of the samples had to be separately prepared. Results The mean particle size of the ULS was 66.1 nm, and the biodistribution of CLS concentrations in various organs, in rank order of magnitude, was liver > kidney > small intestine > other. The biodistribution of FLS concentrations was liver > spleen > lung > other. These rank orders show that synthesized SPION mainly accumulates in the liver. The differences in the distribution were caused by the SPION metabolism. Radiolabeled polymer was metabolized by the kidney and excreted mainly in the urine; [59Fe] was recycled for erythrocyte production in the spleen and excreted mainly in the feces. The MR image of the liver after intravenous injection demonstrated that [Fe] effectively accumulated in the liver and exhibited high-contrast enhancement on T2-weighted images. Conclusion This newly synthesized, polymer-coated SPION appears to be a promising candidate for use as a liver-targeted, biocompatible iron oxide MR imaging agent. PMID:24204138

Comparison of magnetic properties and high-temperature phase stability of phosphate- and oleic acid-capped iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Muthukumaran, T.; Pati, S. S.; Singh, L. H.; de Oliveira, A. C.; Garg, V. K.; Philip, John

2018-03-01

We study the influence of dynamic capping of Fe3O4 nanoparticles with phosphate and oleic acid, on their structure, magnetic properties and thermal stability of magnetic nanoparticles. It is observed that the phosphate coating on iron oxide lowers the dipole-dipole interaction significantly, as compared to oleic acid capping. The Mössbauer results show that the spin canting order of oxidized shell and the mean hyperfine field values follow the order Fe0 (uncoated) > FeOA (oleic acid capped) > FP1 (phosphate capped). The uncoated Fe3O4 nanoparticle is non-stoichiometric in nature due to oxidation, whereas FP1 and FeOA are of the correct stoichiometry. Mössbauer and photoacoustic spectroscopic studies on air-annealed phosphate-coated magnetite nanoparticles confirm that the magnetic iron oxide phase is preserved up to 833 K and a complete conversion of Fe3O4 into the non-magnetic hematite phase occurs at 1173 K. The iron oxide air annealed at 833 K is found to have a shell of orthorhombic α-Fe2O3 over the magnetite core. However, in oleic acid-coated nanoparticles, the magnetic to non-magnetic phase transformation commences at 623 K and the conversion was complete at 823 K. The photoacoustic spectra of the air-annealed phosphate-coated Fe3O4 particles showed a flipping of the absorption intensity between 500-700 nm and 800-1000 nm, due to the conversion of Fe3O4 to γ-Fe2O3 at 923 and γ-Fe2O3 to α-Fe2O3 at 1173 K, respectively. The γ-Fe2O3 showed an intense absorption peak above 750 nm, whereas the α-Fe2O3 showed a peak broadening in the wavelength range of 600-700 nm, in addition to the strong peaks at a wavelength above 750 nm. This study suggests that the photoacoustic spectroscopy can distinguish clearly the three polymorphs of iron oxide i.e., Fe3O4, γ-Fe2O3 and α-Fe2O3. Our results confirm the ability of phosphate-capped iron oxide particles to retard the oxidation of Fe2+ contents during the crystal growth process.

Spectral characteristics of the iron oxides with application to the Martian bright region mineralogy

NASA Technical Reports Server (NTRS)

Sherman, D. M.; Burns, R. G.; Mee Burns, V.

1982-01-01

Reflectance spectra of eight polymorphs of FeOOH and Fe2O3 are determined in order to clarify the nature and significance of the iron oxide mineralogy on Mars. The effect of other components that might interfere with iron oxide absorption features is qualitatively constrained through the use of the Kebulka-Munk theory. It is found that the effect of temperature complicates the identification of a given Fe(3+) phase based on the position of the 6A1-4T1 absorption feature. While the Fe(3+) crystal field transitions are spin forbidden, most of the iron oxide polymorphs exhibit anomalously intense crystal field absorption features due to magnetic coupling between adjacent FeO6 octahedra. It is suggested that the resulting deviations from observed remotely sensed reflectance spectra of Mars may provide a basis for the exclusion of many iron oxide phases as significant components of the Martian Fe(3+) mineralogy. A comparison of these results with the visible region spectra of Martian bright regions indicates that the predominant Fe(3+)-bearing phase may be a magnetically disordered material, such as amorphous gels, some ferric sulphates, and other minerals in which Fe(3+) ions in the crystal structure are not magnetically coupled.

The genome sequence of the metal-mobilizing, extremely thermoacidophilic archaeon Metallosphaera sedula provides insights into bioleaching-associated metabolism.

PubMed

Auernik, Kathryne S; Maezato, Yukari; Blum, Paul H; Kelly, Robert M

2008-02-01

Despite their taxonomic description, not all members of the order Sulfolobales are capable of oxidizing reduced sulfur species, which, in addition to iron oxidation, is a desirable trait of biomining microorganisms. However, the complete genome sequence of the extremely thermoacidophilic archaeon Metallosphaera sedula DSM 5348 (2.2 Mb, approximately 2,300 open reading frames [ORFs]) provides insights into biologically catalyzed metal sulfide oxidation. Comparative genomics was used to identify pathways and proteins involved (directly or indirectly) with bioleaching. As expected, the M. sedula genome contains genes related to autotrophic carbon fixation, metal tolerance, and adhesion. Also, terminal oxidase cluster organization indicates the presence of hybrid quinol-cytochrome oxidase complexes. Comparisons with the mesophilic biomining bacterium Acidithiobacillus ferrooxidans ATCC 23270 indicate that the M. sedula genome encodes at least one putative rusticyanin, involved in iron oxidation, and a putative tetrathionate hydrolase, implicated in sulfur oxidation. The fox gene cluster, involved in iron oxidation in the thermoacidophilic archaeon Sulfolobus metallicus, was also identified. These iron- and sulfur-oxidizing components are missing from genomes of nonleaching members of the Sulfolobales, such as Sulfolobus solfataricus P2 and Sulfolobus acidocaldarius DSM 639. Whole-genome transcriptional response analysis showed that 88 ORFs were up-regulated twofold or more in M. sedula upon addition of ferrous sulfate to yeast extract-based medium; these included genes for components of terminal oxidase clusters predicted to be involved with iron oxidation, as well as genes predicted to be involved with sulfur metabolism. Many hypothetical proteins were also differentially transcribed, indicating that aspects of the iron and sulfur metabolism of M. sedula remain to be identified and characterized.

The Genome Sequence of the Metal-Mobilizing, Extremely Thermoacidophilic Archaeon Metallosphaera sedula Provides Insights into Bioleaching-Associated Metabolism▿ †

PubMed Central

Auernik, Kathryne S.; Maezato, Yukari; Blum, Paul H.; Kelly, Robert M.

2008-01-01

Despite their taxonomic description, not all members of the order Sulfolobales are capable of oxidizing reduced sulfur species, which, in addition to iron oxidation, is a desirable trait of biomining microorganisms. However, the complete genome sequence of the extremely thermoacidophilic archaeon Metallosphaera sedula DSM 5348 (2.2 Mb, ∼2,300 open reading frames [ORFs]) provides insights into biologically catalyzed metal sulfide oxidation. Comparative genomics was used to identify pathways and proteins involved (directly or indirectly) with bioleaching. As expected, the M. sedula genome contains genes related to autotrophic carbon fixation, metal tolerance, and adhesion. Also, terminal oxidase cluster organization indicates the presence of hybrid quinol-cytochrome oxidase complexes. Comparisons with the mesophilic biomining bacterium Acidithiobacillus ferrooxidans ATCC 23270 indicate that the M. sedula genome encodes at least one putative rusticyanin, involved in iron oxidation, and a putative tetrathionate hydrolase, implicated in sulfur oxidation. The fox gene cluster, involved in iron oxidation in the thermoacidophilic archaeon Sulfolobus metallicus, was also identified. These iron- and sulfur-oxidizing components are missing from genomes of nonleaching members of the Sulfolobales, such as Sulfolobus solfataricus P2 and Sulfolobus acidocaldarius DSM 639. Whole-genome transcriptional response analysis showed that 88 ORFs were up-regulated twofold or more in M. sedula upon addition of ferrous sulfate to yeast extract-based medium; these included genes for components of terminal oxidase clusters predicted to be involved with iron oxidation, as well as genes predicted to be involved with sulfur metabolism. Many hypothetical proteins were also differentially transcribed, indicating that aspects of the iron and sulfur metabolism of M. sedula remain to be identified and characterized. PMID:18083856

Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

PubMed

Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

2015-04-28

Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption. Copyright © 2015 Elsevier B.V. All rights reserved.

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: significant influence of the order of combining aryl Grignard reagents with titanate.

PubMed

Liu, Kun Ming; Wei, Juan; Duan, Xin Fang

2015-03-18

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant.

Magnetic order close to superconductivity in the iron-based layered LaO1-xFxFeAs systems

NASA Astrophysics Data System (ADS)

de La Cruz, Clarina; Huang, Q.; Lynn, J. W.; Li, Jiying; , W. Ratcliff, II; Zarestky, J. L.; Mook, H. A.; Chen, G. F.; Luo, J. L.; Wang, N. L.; Dai, Pengcheng

2008-06-01

Following the discovery of long-range antiferromagnetic order in the parent compounds of high-transition-temperature (high-Tc) copper oxides, there have been efforts to understand the role of magnetism in the superconductivity that occurs when mobile `electrons' or `holes' are doped into the antiferromagnetic parent compounds. Superconductivity in the newly discovered rare-earth iron-based oxide systems ROFeAs (R, rare-earth metal) also arises from either electron or hole doping of their non-superconducting parent compounds. The parent material LaOFeAs is metallic but shows anomalies near 150K in both resistivity and d.c. magnetic susceptibility. Although optical conductivity and theoretical calculations suggest that LaOFeAs exhibits a spin-density-wave (SDW) instability that is suppressed by doping with electrons to induce superconductivity, there has been no direct evidence of SDW order. Here we report neutron-scattering experiments that demonstrate that LaOFeAs undergoes an abrupt structural distortion below 155K, changing the symmetry from tetragonal (space group P4/nmm) to monoclinic (space group P112/n) at low temperatures, and then, at ~137K, develops long-range SDW-type antiferromagnetic order with a small moment but simple magnetic structure. Doping the system with fluorine suppresses both the magnetic order and the structural distortion in favour of superconductivity. Therefore, like high-Tc copper oxides, the superconducting regime in these iron-based materials occurs in close proximity to a long-range-ordered antiferromagnetic ground state.

Iron oxide inside SBA-15 modified with amino groups as reusable adsorbent for highly efficient removal of glyphosate from water

NASA Astrophysics Data System (ADS)

Fiorilli, Sonia; Rivoira, Luca; Calì, Giada; Appendini, Marta; Bruzzoniti, Maria Concetta; Coïsson, Marco; Onida, Barbara

2017-07-01

Iron oxide clusters were incorporated into amino-functionalized SBA-15 in order to obtain a magnetically recoverable adsorbent. The physical-chemical properties of the material were characterized by FE-SEM, STEM, XRD, TGA, XPS, FT-IR and acid-base titration analysis. Iron oxide nanoparticles were uniformly dispersed into the pore of mesoporous silica and that the adsorbent is characterized high specific surface area (177 m2/g) and accessible porosity. The sorbent was successfully tested for the removal of glyphosate in real water matrices. Despite the significant content of inorganic ions, a quantitative removal of the contaminant was found. The complete regeneration of the sorbent after the adsorption process through diluted NaOH solution was also proved.

Hydrogen sulfide removal from sediment and water in box culverts/storm drains by iron-based granules.

PubMed

Sun, J L; Shang, C; Kikkert, G A

2013-01-01

A renewable granular iron-based technology for hydrogen sulfide removal from sediment and water in box culverts and storm drains is discussed. Iron granules, including granular ferric hydroxide (GFH), granular ferric oxide (GFO) and rusted waste iron crusts (RWIC) embedded in the sediment phase removed aqueous hydrogen sulfide formed from sedimentary biological sulfate reduction. The exhausted iron granules were exposed to dissolved oxygen and this regeneration process recovered the sulfide removal capacities of the granules. The recovery is likely attributable to the oxidation of the ferrous iron precipitates film and the formation of new reactive ferric iron surface sites on the iron granules and sand particles. GFH and RWIC showed larger sulfide removal capacities in the sediment phase than GFO, likely due to the less ordered crystal structures on their surfaces. This study demonstrates that the iron granules are able to remove hydrogen sulfide from sediment and water in box culverts and storm drains and they have the potential to be regenerated and reused by contacting with dissolved oxygen.

Preservation of protein globules and peptidoglycan in the mineralized cell wall of nitrate-reducing, iron(II)-oxidizing bacteria: a cryo-electron microscopy study.

PubMed

Miot, J; Maclellan, K; Benzerara, K; Boisset, N

2011-11-01

Iron-oxidizing bacteria are important actors of the geochemical cycle of iron in modern environments and may have played a key role all over Earth's history. However, in order to better assess that role on the modern and the past Earth, there is a need for better understanding the mechanisms of bacterial iron oxidation and for defining potential biosignatures to be looked for in the geologic record. In this study, we investigated experimentally and at the nanometre scale the mineralization of iron-oxidizing bacteria with a combination of synchrotron-based scanning transmission X-ray microscopy (STXM), scanning transmission electron microscopy (STEM) and cryo-transmission electron microscopy (cryo-TEM). We show that the use of cryo-TEM instead of conventional microscopy provides detailed information of the successive iron biomineralization stages in anaerobic nitrate-reducing iron-oxidizing bacteria. These results suggest the existence of preferential Fe-binding and Fe-oxidizing sites on the outer face of the plasma membrane leading to the nucleation and growth of Fe minerals within the periplasm of these cells that eventually become completely encrusted. In contrast, the septa of dividing cells remain nonmineralized. In addition, the use of cryo-TEM offers a detailed view of the exceptional preservation of protein globules and the peptidoglycan within the Fe-mineralized cell walls of these bacteria. These organic molecules and ultrastructural details might be protected from further degradation by entrapment in the mineral matrix down to the nanometre scale. This is discussed in the light of previous studies on the properties of Fe-organic interactions and more generally on the fossilization of mineral-organic assemblies. © 2011 Blackwell Publishing Ltd.

Defluoridation by Bacteriogenic Iron Oxides: Sorption Studies

NASA Astrophysics Data System (ADS)

Evans, K.; Ferris, F.

2009-05-01

At concentrations above 1 mg/L, fluoride in drinking water can lead to dental and skeletal fluorosis, a disease that causes mottling of the teeth, calcification of ligaments, crippling bone deformities and many other physiological disorders that can, ultimately, lead to death. Conservative estimates are that fluorosis afflicts tens of millions of people worldwide. As there is no treatment for fluorosis, prevention is the only means of controlling the disease. While numerous defluoridation techniques have been explored, no single method has been found to be both effective and inexpensive enough to implement widely. Our research began in India, with a large-scale geochemical study of the groundwater in a fluoride-contaminated region of Orissa. Having developed a better understanding of the geochemical relationships that exist between fluoride and other parameters present in an affected area, as well as the complex relationships that arise among those parameters that can impact the presence of fluoride, we began investigating certain remediation scenarios involving iron oxides. A common approach to remediation involves the partitioning of fluoride from groundwater by sorption onto a variety of materials, one of the most effective of which is iron oxide whose surface area acts as a scavenger for fluoride. In the presence of iron oxidizing bacteria, the oxidation rate of iron has been shown to be ˜6 times greater than in their absence; fluoride should, therefore, be removed from an aqueous environment by bacteriogenic iron oxides (BIOS) much more quickly than by abiotic iron oxides. Most recently, sorption studies have been conducted using both BIOS and synthetic hydrous ferric oxides in order to compare the behavior between biotic and abiotic sorbents. These studies have provided sorption isotherms that allow comparison of fluoride removed by sorption to BIOS versus synthetic iron oxides. Sorption affinity constants have also been determined, which allow for the prediction of fluoride removal in a wide variety of groundwater systems. Sorption isotherms and affinity constants show the use of BIOS to be a promising technique for the remediation of fluoride in groundwater.

AN INVESTIGATION OF ARSENIC MOBILITY FROM IRON OXIDE SOLIDS PRODUCED DURING DRINKING WATER TREATMENT

EPA Science Inventory

The Arsenic Rule under the Safe Drinking Water Act will require certain drinking water suppliers to add to or modify their existing treatment in order to comply with the regulations. One of the treatment options is iron co-precipitation. This treatment is attractive because ars...

ARSENIC MOBILITY FROM IRON OXIDE SOLIDS PRODUCED DURING WATER TREATMENT

EPA Science Inventory

The Arsenic Rule under the Safe Drinking Water Act will require certain drinking water suppliers to add to or modify their existing treatment in order to comply with the new 10 ppb arsenic standard. One of the treatment options is co-precipitation of arsenic with iron. This tre...

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

Beam, Jake; Bernstein, Hans C.; Jay, Z.

Iron oxide microbial mats are ubiquitous geobiological features on Earth and occur in extant acidic hot springs of Yellowstone National Park (YNP), WY, USA, and form as a result of microbial processes. The relative contribution of different organisms to the development of these mat ecosystems is of specific interest. We hypothesized that chemolithoautotrophic organisms contribute to the early development and production of Fe(III)-oxide mats, which could support later-colonizing heterotrophic microorganisms. Sterile glass slides were incubated in the outflow channels of two acidic geothermal springs in YNP, and spatiotemporal changes in Fe(III)-oxide accretion and abundance of relevant community members were measured.more » Lithoautotrophic Hydrogenobaculum spp. were first colonizers and the most abundant taxa identified during early successional stages (7 – 40 days). Populations of M. yellowstonensis colonized after ~ 7 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized after 30 days, and emerge as the dominant functional guild in mature iron oxide mats (1 – 2 cm thick) that form after 70 – 120 days. First-order rate constants of iron oxide accretion ranged from 0.05 – 0.046 day-1, and reflected the absolute amount of iron accreted. Micro- and macroscale microterracettes were identified during iron oxide mat development, and suggest that the mass transfer of oxygen limits microbial growth. This was also demonstrated using microelectrode measurements of oxygen as a function of mat depth, which showed steep gradients in oxygen from the aqueous mat interface to ~ 1 mm. The formation and succession of amorphous Fe(III)-oxide mat communities follows a predictable pattern of distinct stages and growth. The successional stages and microbial signatures observed in these extant Fe(III)-oxide mat communities may be relevant to other past or present Fe(III)-oxide mineralizing systems.« less

Solid-stabilized emulsion formation using stearoyl lactylate coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Vengsarkar, Pranav S.; Roberts, Christopher B.

2014-10-01

Iron oxide nanoparticles can exhibit highly tunable physicochemical properties that are extremely important in applications such as catalysis, biomedicine and environmental remediation. The small size of iron oxide nanoparticles can be used to stabilize oil-in-water Pickering emulsions due to their high energy of adsorption at the interface of oil droplets in water. The objective of this work is to investigate the effect of the primary particle characteristics and stabilizing agent chemistry on the stability of oil-in-water Pickering emulsions. Iron oxide nanoparticles were synthesized by the co-precipitation method using stoichiometric amounts of Fe2+ and Fe3+ salts. Sodium stearoyl lactylate (SSL), a Food and Drug Administration approved food additive, was used to functionalize the iron oxide nanoparticles. SSL is useful in the generation of fat-in-water emulsions due to its high hydrophilic-lipophilic balance and its bilayer-forming capacity. Generation of a monolayer or a bilayer coating on the nanoparticles was controlled through systematic changes in reagent concentrations. The coated particles were then characterized using various analytical techniques to determine their size, their crystal structure and surface functionalization. The capacity of these bilayer coated nanoparticles to stabilize oil-in-water emulsions under various salt concentrations and pH values was also systematically determined using various characterization techniques. This study successfully demonstrated the ability to synthesize iron oxide nanoparticles (20-40 nm) coated with SSL in order to generate stable Pickering emulsions that were pH-responsive and resistant to significant destabilization in a saline environment, thereby lending themselves to applications in advanced oil spill recovery and remediation.

A predictive model of iron oxide nanoparticles flocculation tuning Z-potential in aqueous environment for biological application

NASA Astrophysics Data System (ADS)

Baldassarre, Francesca; Cacciola, Matteo; Ciccarella, Giuseppe

2015-09-01

Iron oxide nanoparticles are the most used magnetic nanoparticles in biomedical and biotechnological field because of their nontoxicity respect to the other metals. The investigation of iron oxide nanoparticles behaviour in aqueous environment is important for the biological applications in terms of polydispersity, mobility, cellular uptake and response to the external magnetic field. Iron oxide nanoparticles tend to agglomerate in aqueous solutions; thus, the stabilisation and aggregation could be modified tuning the colloids physical proprieties. Surfactants or polymers are often used to avoid agglomeration and increase nanoparticles stability. We have modelled and synthesised iron oxide nanoparticles through a co-precipitation method, in order to study the influence of surfactants and coatings on the aggregation state. Thus, we compared experimental results to simulation model data. The change of Z-potential and the clusters size were determined by Dynamic Light Scattering. We developed a suitable numerical model to predict the flocculation. The effects of Volume Mean Diameter and fractal dimension were explored in the model. We obtained the trend of these parameters tuning the Z-potential. These curves matched with the experimental results and confirmed the goodness of the model. Subsequently, we exploited the model to study the influence of nanoparticles aggregation and stability by Z-potential and external magnetic field. The highest Z-potential is reached up with a small external magnetic influence, a small aggregation and then a high suspension stability. Thus, we obtained a predictive model of Iron oxide nanoparticles flocculation that will be exploited for the nanoparticles engineering and experimental setup of bioassays.

The special features of the crystal structure and properties of oxides with mixed conductivity based on lanthanum gallate

NASA Astrophysics Data System (ADS)

Politova, E. D.; Ivanov, S. A.; Kaleva, G. M.; Mosunov, A. V.; Rusakov, V. S.

2008-10-01

The paper presents a review of works on the synthesis, structural composition effects, phase transitions, and electrical conductivity properties of multicomponent solid solutions based on heterosubstituted lanthanum gallate (La,A)(Ga,M)O3 - y . High-temperature phase transitions and structural and charge ordering effects were studied. The presence of iron cations in different valence states was proved; the relative contents of these cations depended on the x parameter and nonstoichiometry parameter y of the base composition. For M = Fe, antiferromagnetic ordering was observed; its temperature interval was determined by the concentration of iron cations in the high-spin state. The total conductivity was found to increase as the concentration of transition metal cations grew because of an increase in the electronic conductivity component. The data on structural parameters and dc and ac conductivity substantiated the conclusion that the highest ionic conductivity and permeability to oxygen were characteristic of iron-containing oxides. The results obtained are evidence that crystal chemical factors play a determining role in the formation of the ion-conducting properties of anion-deficient perovskite-like oxides.

Magnetic and gravity gradiometry framework for Mesoproterozoic iron oxide-apatite and iron oxide-copper-gold deposits, southeast Missouri, USA

USGS Publications Warehouse

McCafferty, Anne E.; Phillips, Jeffrey; Driscoll, Rhonda L.

2016-01-01

High-resolution airborne magnetic and gravity gradiometry data provide the geophysical framework for evaluating the exploration potential of hidden iron oxide deposits in Mesoproterozoic basement rocks of southeast Missouri. The data are used to calculate mineral prospectivity for iron oxide-apatite (IOA) ± rare earth element (REE) and iron oxide-copper-gold (IOCG) deposits. Results delineate the geophysical footprints of all known iron oxide deposits and reveal several previously unrecognized prospective areas. The airborne data are also inverted to three-dimensional density and magnetic susceptibility models over four concealed deposits at Pea Ridge (IOA ± REE), Boss (IOCG), Kratz Spring (IOA), and Bourbon (IOCG). The Pea Ridge susceptibility model shows a magnetic source that is vertically extensive and traceable to a depth of greater than 2 km. A smaller density source, located within the shallow Precambrian basement, is partly coincident with the magnetic source at Pea Ridge. In contrast, the Boss models show a large (625-m-wide), vertically extensive, and coincident dense and magnetic stock with shallower adjacent lobes that extend more than 2,600 m across the shallow Precambrian paleosurface. The Kratz Spring deposit appears to be a smaller volume of iron oxides and is characterized by lower density and less magnetic rock compared to the other iron deposits. A prospective area identified south of the Kratz Spring deposit shows the largest volume of coincident dense and nonmagnetic rock in the subsurface, and is interpreted as prospective for a hematite-dominant lithology that extends from the top of the Precambrian to depths exceeding 2 km. The Bourbon deposit displays a large bowl-shaped volume of coincident high density and high-magnetic susceptibility rock, and a geometry that suggests the iron mineralization is vertically restricted to the upper parts of the Precambrian basement. In order to underpin the evaluation of the prospectivity and three-dimensional models, an extensive statistical summary of density and apparent magnetic susceptibility measurements is presented that includes data on several hundred samples taken from the deposits, altered wall rocks, and unaltered country rocks.

The secret behind the success of doping nickel oxyhydroxide with iron.

PubMed

Fidelsky, Vicky; Toroker, Maytal Caspary

2017-03-15

Discovering better catalysts for water splitting is the holy grail of the renewable energy field. One of the most successful water oxidation catalysts is nickel oxyhydroxide (NiOOH), which is chemically active only as a result of doping with Fe. In order to shed light on how Fe improves efficiency, we perform Density Functional Theory +U (DFT+U) calculations of water oxidation reaction intermediates of Fe substitutional doped NiOOH. The results are analyzed while considering the presence of vacancies that we use as probes to test the effect of adding charge to the surface. We find that the smaller electronegativity of the Fe dopant relative to Ni allows the dopant to have several possible oxidation states with less energy penalty. As a result, the presence of vacancies which alters local oxidation states does not affect the low overpotential of Fe-doped NiOOH. We conclude that the secret to the success of doping NiOOH with iron is the ability of iron to easily change oxidation states, which is critical during the chemical reaction of water oxidation.

Enhanced Adsorption of Selenium Ions from Aqueous Solution Using Iron Oxide Impregnated Carbon Nanotubes

PubMed Central

Bakather, Omer Y.; Khraisheh, Majeda; Nasser, Mustafa S.

2017-01-01

The aim of this research was to investigate the potential of raw and iron oxide impregnated carbon nanotubes (CNTs) as adsorbents for the removal of selenium (Se) ions from wastewater. The original and modified CNTs with different loadings of Fe2O3 nanoparticles were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffractometer (XRD), Brunauer, Emmett, and Teller (BET) surface area analyzer, thermogravimetric analysis (TGA), zeta potential, and energy dispersive X-ray spectroscopy (EDS). The adsorption parameters of the selenium ions from water using raw CNTs and iron oxide impregnated carbon nanotubes (CNT-Fe2O3) were optimized. Total removal of 1 ppm Se ions from water was achieved when 25 mg of CNTs impregnated with 20 wt.% of iron oxide nanoparticles is used. Freundlich and Langmuir isotherm models were used to study the nature of the adsorption process. Pseudo-first and pseudo-second-order models were employed to study the kinetics of selenium ions adsorption onto the surface of iron oxide impregnated CNTs. Maximum adsorption capacity of the Fe2O3 impregnated CNTs, predicted by Langmuir isotherm model, was found to be 111 mg/g. This new finding might revolutionize the adsorption treatment process and application by introducing a new type of nanoadsorbent that has super adsorption capacity towards Se ions. PMID:28555093

Effects of pore topology and iron oxide core on doxorubicin loading and release from mesoporous silica nanoparticles

NASA Astrophysics Data System (ADS)

Ronhovde, Cicily J.; Baer, John; Larsen, Sarah C.

2017-06-01

Mesoporous silica nanoparticles (MSNs) have a network of pores that give rise to extremely high specific surface areas, making them attractive materials for applications such as adsorption and drug delivery. The pore topology can be readily tuned to achieve a variety of structures such as the hexagonally ordered Mobil Crystalline Material 41 (MCM-41) and the disordered "wormhole" (WO) mesoporous silica (MS) structure. In this work, the effects of pore topology and iron oxide core on doxorubicin loading and release were investigated using MSNs with pore diameters of approximately 3 nm and sub-100 nm particle diameters. The nanoparticles were loaded with doxorubicin, and the drug release into phosphate-buffered saline (PBS, 10 mM, pH 7.4) at 37 °C was monitored by fluorescence spectroscopy. The release profiles were fit using the Peppas model. The results indicated diffusion-controlled release for all samples. Statistically significant differences were observed in the kinetic host-guest parameters for each sample due to the different pore topologies and the inclusion of an iron oxide core. Applying a static magnetic field to the iron oxide core WO-MS shell materials did not have a significant impact on the doxorubicin release. This is the first time that the effects of pore topology and iron oxide core have been isolated from pore diameter and particle size for these materials.

Symmetry and charge order in Fe2OBO3 studied through polarized resonant x-ray diffraction

NASA Astrophysics Data System (ADS)

Bland, S. R.; Angst, M.; Adiga, S.; Scagnoli, V.; Johnson, R. D.; Herrero-Martín, J.; Hatton, P. D.

2010-09-01

Bond valence sum calculations have previously suggested that iron oxyborate exhibits charge order of the Fe ions with integer 2+/3+ valence states. Meanwhile transition metal oxides typically show much smaller, fractional charge disproportionations. Using resonant x-ray diffraction at the iron K edge, we find resonant features which are much larger than those ordinarily observed in charge ordered oxides. Simulations were subsequently performed using a cluster-based, monoelectronic code. The nanoscale domain structure prevents precise fitting; nevertheless the simulations confirm the diagonal charge order symmetry, as well as the unusually large charge disproportionation. We have demonstrated the conversion of linearly to nonlinearly polarized light and vice versa through full polarization analysis. Simulations show that this effect principally results from interference between the isotropic and anisotropic scattering terms. This mechanism is likely to account for similar observations in alternative systems.

Removal of Iron Oxide Scale from Feed-water in Thermal Power Plant by Using Magnetic Separation

NASA Astrophysics Data System (ADS)

Nakanishi, Motohiro; Shibatani, Saori; Mishima, Fumihito; Akiyama, Yoko; Nishijima, Shigehiro

2017-09-01

One of the factors of deterioration in thermal power generation efficiency is adhesion of the scale to inner wall in feed-water system. Though thermal power plants have employed All Volatile Treatment (AVT) or Oxygen Treatment (OT) to prevent scale formation, these treatments cannot prevent it completely. In order to remove iron oxide scale, we proposed magnetic separation system using solenoidal superconducting magnet. Magnetic separation efficiency is influenced by component and morphology of scale which changes their property depending on the type of water treatment and temperature. In this study, we estimated component and morphology of iron oxide scale at each equipment in the feed-water system by analyzing simulated scale generated in the pressure vessel at 320 K to 550 K. Based on the results, we considered installation sites of the magnetic separation system.

Method for preparing hydrous iron oxide gels and spherules

DOEpatents

Collins, Jack L.; Lauf, Robert J.; Anderson, Kimberly K.

2003-07-29

The present invention is directed to methods for preparing hydrous iron oxide spherules, hydrous iron oxide gels such as gel slabs, films, capillary and electrophoresis gels, iron monohydrogen phosphate spherules, hydrous iron oxide spherules having suspendable particles homogeneously embedded within to form composite sorbents and catalysts, iron monohydrogen phosphate spherules having suspendable particles of at least one different sorbent homogeneously embedded within to form a composite sorbent, iron oxide spherules having suspendable particles homogeneously embedded within to form a composite of hydrous iron oxide fiber materials, iron oxide fiber materials, hydrous iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, iron oxide fiber materials having suspendable particles homogeneously embedded within to form a composite, dielectric spherules of barium, strontium, and lead ferrites and mixtures thereof, and composite catalytic spherules of barium or strontium ferrite embedded with oxides of Mg, Zn, Pb, Ce and mixtures thereof. These variations of hydrous iron oxide spherules and gel forms prepared by the gel-sphere, internal gelation process offer more useful forms of inorganic ion exchangers, catalysts, getters, dielectrics, and ceramics.

Investigation of Redox Metal Oxides for Carbonaceous Fuel Conversion and CO2 Capture

NASA Astrophysics Data System (ADS)

Galinsky, Nathan Lee

The chemical looping combustion (CLC) process uses metal oxides, also referred to as oxygen carriers, in a redox scheme for conversion of carbonaceous fuels into a concentrated stream of CO2 and steam while also producing heat and electricity. The unique redox scheme of CLC allows CO2 capture with minimal energy penalty. The CLC process performance greatly depends on the oxygen carrier that is chosen. To date, more than 1000 oxygen carriers have been developed for chemical-looping processes using metal oxides containing first-row transition metals. Oxygen carriers are typically mixed with an inert ceramic support to improve their overall mechanical stability and recyclability. This study focuses on design of (i) iron oxide oxygen carriers for conversion of gaseous carbonaceous fuels and (ii) development of perovskite CaMnO 3-d with improved stability and redox properties for conversion of solid fuels. Iron oxide is cheap and environmentally benign. However, it suffers from low activity with carbonaceous fuels due partially to the low ionic conductivity of iron oxides. In order to address the low activity of iron-oxide-based oxygen carriers, support addition has been shown to lower the energy barrier of oxygen anion transport within the oxygen carrier. This work adds a mixed-ionic-and-electronic-conductor (MIEC) support to iron oxide to help facilitate O2- transport inside the lattice of iron oxide. The MIEC-supported iron oxide is compared to commonly used supports including TiO2 and Al2O 3 and the pure ionic conductor support yttria-stabilized zirconia (YSZ) for conversion of different carbonaceous fuels and hydrogen. Results show that the MIEC-supported iron oxide exhibits up to 70 times higher activity than non-MIEC-supported iron oxides for methane conversion. The MIEC supported iron oxide also shows good recyclability with only minor agglomeration and carbon formation observed. The effect of support-iron oxide synergies is further investigated to understand other physical and chemical properties that lead to highly active and recyclable oxygen carriers. Perovskite and fluorite-structured MIEC supports are tested for conversion of methane. The perovskite supported iron oxides exhibit higher activity and stability resulting from the high mixed conductivity of the support. Fluorite-structured CeO2 oxygen carriers deactivated by 75% after 10 redox cycles. This deactivation was attributed to agglomeration of iron oxide. The agglomeration was determined to occur due to Fe x+ transport during the oxidation step leading to high content of Fe on the surface of the oxygen carrier. Besides the MIEC supports, inert MgAl2O4 supported iron oxide is observed to activate in methane. The activation is attributed to carbon formation causing physical degradation of the oxygen carrier and leading to higher surface area and porosity. To achieve high activity with solid fuels, chemical looping with oxygen uncoupling (CLOU) is commonly used. This process uses oxygen carriers with high PO2 that allows the oxygen carrier to release a portion of their lattice oxygen as gaseous oxygen. In turn, the gaseous oxygen can react with solid fuel particles at a higher rate than the lattice oxygen. CaMnO 3 perovskite oxygen carriers offer high potential for CLOU. However, pure CaMnO3 suffers from long-term recyclability and sulfur poisoning. Addition of A-site (Ba and Sr) and B-site (Fe, Ni, Co, Al, and V) dopants are used to improve the performance of the base CaMnO3 oxygen carrier. Sr (A-site) and Fe (B-site) exhibit high compatibility with the base perovskite structure. Both dopants observe oxygen uncoupling properties up to 200°C below that of pure CaMnO3. Additionally, the doped structures also exhibit higher stability at high temperatures (>1000°C) and during redox cycles. The doped oxygen carriers also demonstrate significantly improved activity for coal char conversion.

Size-dependent cytotoxicity and inflammatory responses of PEGylated silica-iron oxide nanocomposite size series

NASA Astrophysics Data System (ADS)

Injumpa, Wishulada; Ritprajak, Patcharee; Insin, Numpon

2017-04-01

Iron oxides nanoparticles have been utilized in biological systems and biomedical applications for many years because they are relatively safe and stable comparing to other magnetic nanomaterials. In some applications, iron oxide nanoparticles were modified with silica in order to be more stable in biological systems and able to be functionalized with various functional groups. Moreover, poly(ethylene glycol) (PEG) was one on the most used polymer to graft onto the nanoparticles in order to increase their biocompatibility, dispersibility and stability in aqueous solutions. Therefore, the nanocomposites comprising iron oxide nanoparticles, silica, and PEG could become multifunctional carriers combining superparamagnetic character, multi-functionality and high stability in biological environments. Herein, we reported the preparation of the nanocomposites and effects of their sizes on cytotoxicity and inflammatory responses. The PEGylated silica-iron oxide nanocomposites were prepared by coating of poly(poly(ethylene glycol) monomethyl ether methacrylate) (PPEGMA) on magnetic nanoparticle-silica nanocomposites via Atom Transfer Radical Polymerization (ATRP). The iron oxide nanoparticles were synthesized using a thermal decomposition method. The silica shells were then coated on iron oxides nanoparticles using reverse microemulsion and sol-gel methods. The size series of the nanocomposites with the diameter of 24.86±4.38, 45.24±5.00, 98.10±8.88 and 202.22±6.70 nm as measured using TEM were obtained. Thermogravimetric analysis (TGA) was used for the determination of % weight of PPEGMA on the nanocomposites showing the weight loss of ranging from 65% for smallest particles to 30% for largest particles. The various sizes (20, 40, 100, 200 nm) and concentrations (10, 100, 1000 μg/mL) of the nanocomposites were tested for their cytotoxicity in fibroblast and macrophage cell lines using MTT assay. The different sizes did not affect cell viability of fibroblast, albeit incubation with the highest concentration of 1000 μg/mL. Although 1000 μg/mL of all sizes of the nanocomposites decreased macrophage viability, the cytotoxicity of the nanocomposites was notably less than silica. The inflammatory response of macrophage was also observed by ELISA, and we found that the size of 20 and 40 nm, but not 100 and 200 nm, obviously stimulated IL-6 production. From this study, the preparations of multifunctional superparamagnetic nanocomposites of different sizes along with the size-dependent effects on cellular toxicity and inflammatory response were demonstrated and could be applied for designing of new drug carriers.

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

Increased endogenous DNA oxidation correlates to increased iron levels in melanocytes relative to keratinocytes.

PubMed

Pelle, Edward; Huang, Xi; Zhang, Qi; Pernodet, Nadine; Yarosh, Daniel B; Frenkel, Krystyna

2014-01-01

The endogenous oxidative state of normal human epidermal melanocytes was investigated and compared to normal human epidermal keratinocytes (NHEKs) in order to gain new insight into melanocyte biology. Previously, we showed that NHEKs contain higher levels of hydrogen peroxide (H2O2) than melanocytes and that it can migrate from NHEKs to melanocytes by passive permeation. Nevertheless, despite lower concentrations of H2O2, we now report higher levels of oxidative DNA in melanocytes as indicated by increased levels of 8-oxo-2'-deoxyguanosine (8-oxo-dG): 4.49 (±0.55 SEM) 8-oxo-dG/10(6) dG compared to 1.49 (±0.11 SEM) 8-oxo-dG/10(6) dG for NHEKs. An antioxidant biomarker, glutathione (GSH), was also lower in melanocytes (3.14 nmoles (±0.15 SEM)/cell) in comparison to NHEKs (5.98 nmoles (±0.33 SEM)/cell). Intriguingly, cellular bioavailable iron as measured in ferritin was found to be nearly fourfold higher in melanocytes than in NHEKs. Further, ferritin levels in melanocytes were also higher than in hepatocarcinoma cells, an iron-rich cell, and it indicates that higher relative iron levels may be characteristic of melanocytes. To account for the increased oxidative DNA and lower GSH and H2O2 levels that we observe, we propose that iron may contribute to higher levels of oxidation by reacting with H2O2 through a Fenton reaction leading to the generation of DNA-reactive hydroxyl radicals. In conclusion, our data support the concept of elevated oxidation and high iron levels as normal parameters of melanocytic activity. We present new evidence that may contribute to our understanding of the melanogenic process and lead to the development of new skin care products.

Biomineralogy and Morphology of the Marine Iron-oxidizing Bacterium Mariprofundus ferrooxydans

NASA Astrophysics Data System (ADS)

Chan, C. S.; Emerson, D.; Edwards, K. J.

2006-12-01

Mariprofundus ferrooxydans strain PV-1 is a lithoautotrophic iron-oxidizing proteobacterium isolated from the Loihi Seamount in Hawaii. As cells grow, they form filaments upon which iron minerals are deposited. Based on similarities in morphology, these structures appear to accumulate and form the bulk of iron mats at Loihi. Furthermore, Mariprofundus has been observed in a number of other seafloor mat samples (e.g. by microscopy and 16S rRNA gene sequencing of East Pacific Rise samples, C. M. Santelli unpublished data), suggesting that the occurrence of Mariprofundus is widespread. To learn about the effect of Mariprofundus on iron cycling, we are studying the processes by which it oxidizes iron and influences iron mineral formation. We are conducting studies on the spatial relationships between the cells, stalks, and minerals using scanning and transmission electron microscopy (SEM and TEM). Identification and imaging of stalk-bound, nanometer-sized iron oxyhydroxide minerals is being performed by high-resolution transmission electron microscopy (HRTEM). We have developed sample preparation methods to preserve in vivo spatial relationships, involving direct colonization of sample holders in cultures and in the environment. Method development has been performed on stalk-forming, iron-oxidizing Gallionella ferruginea cultures and terrestrial iron mats. Gallionella is morphologically and physiologically very similar to Mariprofundus, although 16S rRNA gene phylogeny shows that they are not closely related. Comparison of the terrestrial and marine iron-oxidizing bacteria (FeOB) gives us insight into adaptations that are particular to marine iron-oxidizers and those that are common to all FeOB. Light and fluorescence microscopy of Mariprofundus cultures has shown that a single bean-shaped cell lies at the end of each filament. SEM and TEM results have revealed that the filament is ribbon-like, sometimes twisted as with the classic Gallionella stalk, but sometimes not. Filaments formed in culture have been measured at 0.5 and 1.7 microns in width and as long as 70 microns. They are composed of a varying number of parallel subfilaments, each approximately 70 nm in width. HRTEM observations show that lightly-mineralized filaments are covered in nanometer-size, poorly crystalline, and possibly amorphous iron oxyhydroxides, which likely represent an early stage in filament mineralization. Highly-mineralized filaments are coated in lepidocrocite and akaganeite (both iron oxyhydroxides), in random crystallographic orientations. The more crystalline minerals probably result from recrystallization of the initially-deposited FeOOH and continued precipitation on the filament. We will revisit Loihi in October to collect fresh, undisturbed samples for electron microscopy, in order to compare cultured and natural samples. This work is being performed in conjunction with genomic and protein analyses aimed at identifying the genes involved in iron oxidation.

Effect of adherent bacteria and bacterial extracellular polymers upon assimilation by Macoma balthica of sediment-bound Cd, Zn and Ag

USGS Publications Warehouse

Harvey, Ronald W.; Luoma, Samuel N.

1985-01-01

Effects of adherent bacteria and bacterial extracellular polymer (exopolymer) upon uptake of particle-bound Cd, Zn and Ag by the deposit-feeding clam Macoma balthica were studied in the laboratory. Amorphous iron oxyhydroxide and unaltered and alkaline-extracted sediments were used as model particulates in separate, controlled deposit-feeding experiments. In general, amounts of metal taken up from ingested particles varied dramatically with the nature of the particle surface. Ingestion of contaminated iron oxide particles did not contribute to overall uptake of Cd and Ag in feeding clams, but accounted for 89 to 99% of total Zn uptake. Exopolymer adsorbed on iron oxide particles caused an increase in the biological availability of particle-bound metals in the order Ag>Cd>Zn, whereas adherent bacteria up to 3.2 X 1011 g-1 had no effect upon amounts of metal taken up from ingested particulates. At the higher Cd and Ag concentrations employed (3.6 X 10-7M), feeding rates declined with increasing amounts of iron oxide-bound exopolymer, suggesting behavioral avoidance due to increased metal availability. Much of the Cd (57 %) taken up by clams feeding on unaltered estuarine sediments originated from particulates, even though particle/solute distribution of Cd (86%) was similar to that in experiments with iron oxide particles. Uptake of Cd from alkalineextracted sediments was insignificant, as it was from unamended iron oxide. However, addition of exopolymer (10 mgg-1 sediment) caused a restoration nn bioavailability of sediment-bound Cd.

Design and Fabrication of N-Alkyl-Polyethylenimine-Stabilized Iron Oxide Nanoclusters for Gene Delivery

PubMed Central

Liu, Gang; Wang, Zhiyong; Lee, Seulki; Ai, Hua; Chen, Xiaoyuan

2013-01-01

With the rapid development of nanotechnology, inorganic magnetic nanoparticles, especially iron oxide nanoparticles (IOs), have emerged as great vehicles for biomedical diagnostic and therapeutic applications. In order to rationally design IO-based gene delivery nanovectors, surface modification is essential and determines the loading and release of the gene of interest. Here we highlight the basic concepts and applications of nonviral gene delivery vehicles based on low molecular weight N-alkyl polyethylenimine-stabilized IOs. The experimental protocols related to these topics are described in this chapter. PMID:22568910

Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes.

PubMed

Ntim, Susana Addo; Mitra, Somenath

2011-05-12

This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L(-1). The absorption capacity of the composite was 1723 µg g(-1) and 189 µg g(-1) for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models.

Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

NASA Technical Reports Server (NTRS)

Burns, R. G.; Martinez, S. L.

1991-01-01

Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

Oxidant Selection for the Treatment of Manganese (II), Iron (II), and Arsenic (III) in Groundwaters

EPA Science Inventory

In order to comply with the United States Environmental Protection Agency’s (U.S. EPA’s) arsenic standard and the manganese and iron secondary maximum contaminant levels (MCLs) in water (10µg/L, 50µg/L, and 300µg/L, respectively), many Midwestern water utilities must add a strong...

Fabrication of nanoparticles using Annona squamosa leaf and assessment of its effect on liver (Hep G2) cancer cell line

NASA Astrophysics Data System (ADS)

Vanitha, V.; Hemalatha, S.; Pushpabharathi, N.; Amudha, P.; Jayalakshmi, M.

2017-04-01

Annona squamosa is a fruit bearing plant possesses potent bioactive compounds in all its part. In this present investigation iron oxide nanoparticle was synthesized from hydroethanol extract of Annona squamosa leaves at 60°C temperature. Production of iron oxide nanoparticles in extraction is detected by UV-V spectrophotometer, Scanning electron microscopy was employed to analyse the structure of nanoparticles. Fourier transform infrared spectroscopy (FT-IR) analysis were performed, in order to determine the functional groups on Annona squamosa leaves extract. The synthesized Fe3O4 NPs shows potential cytotoxicity against liver carcinoma cell line (HepG2), and there is no toxicity on the normal liver cell line. Our reports confirmed that the Annona squamosa leaf is a very good eco-friendly and nontoxic bioreductant for the synthesis of Iron oxide nanoparticle and opens up further opportunities for fabrication of drugs towards cancer therapy.

Biomolecular crystals for material applications and a mechanistic study of an iron oxide nanoparticle synthesis

NASA Astrophysics Data System (ADS)

Falkner, Joshua Charles

The three projects within this work address the difficulties of controlling biomolecular crystal formats (i.e. size and shape), producing 3-D ordered composite materials from biomolecular crystal templates, and understanding the mechanism of a practical iron oxide synthesis. The unifying thread consistent throughout these three topics is the development of methods to manipulate nanomaterials using a bottom-up approach. Biomolecular crystals are nanometer to millimeter sized crystals that have well ordered mesoporous solvent channels. The overall physical dimensions of these crystals are highly dependent on crystallization conditions. The controlled growth of micro- and nanoprotein crystals was studied to provide new pathways for creating smaller crystalline protein materials. This method produced tetragonal hen egg-white lysozyme crystals (250--100,000 nm) with near monodisperse size distributions (<15%). With this degree of control, existing protein crystal applications such as drug delivery and analytical sensors can reach their full potential. Applications for larger crystals with inherently ubiquitous pore structures could extend to materials used for membranes or templates. In this work, the porous structure of larger cowpea mosaic virus crystals was used to template metal nanoparticle growth within the body centered cubic crystalline network. The final composite material was found to have long range ordering of palladium and platinum nonocrystal aggregates (10nm) with symmetry consistent to the virus template. Nanoparticle synthesis itself is an immense field of study with an array of diverse applications. The final piece of this work investigates the mechanism behind a previously developed iron oxide synthesis to gain more understanding and direction to future synthesis strategies. The particle growth mechanism was found to proceed by the formation of a solvated iron(III)oleate complex followed by a reduction of iron (III) to iron (II). This unstable iron(II) nucleates to form a wustite (FeO) core which serves as an epitaxial surface for the magnetite (Fe3O4) shell growth. This method produces spherical particles (6-60nm) with relative size distributions of less than 15%.

Effects of anodizing conditions and annealing temperature on the morphology and crystalline structure of anodic oxide layers grown on iron

NASA Astrophysics Data System (ADS)

Pawlik, Anna; Hnida, Katarzyna; Socha, Robert P.; Wiercigroch, Ewelina; Małek, Kamilla; Sulka, Grzegorz D.

2017-12-01

Anodic iron oxide layers were formed by anodization of the iron foil in an ethylene glycol-based electrolyte containing 0.2 M NH4F and 0.5 M H2O at 40 V for 1 h. The anodizing conditions such as electrolyte composition and applied potential were optimized. In order to examine the influence of electrolyte stirring and applied magnetic field, the anodic samples were prepared under the dynamic and static conditions in the presence or absence of magnetic field. It was shown that ordered iron oxide nanopore arrays could be obtained at lower anodizing temperatures (10 and 20 °C) at the static conditions without the magnetic field or at the dynamic conditions with the applied magnetic field. Since the as-prepared anodic layers are amorphous in nature, the samples were annealed in air at different temperatures (200-500 °C) for a fixed duration of time (1 h). The morphology and crystal phases developed after anodization and subsequent annealing were characterized using field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The results proved that the annealing process transforms the amorphous layer into magnetite and hematite phases. In addition, the heat treatment results in a substantial decrease in the fluorine content and increase in the oxygen content.

Nitric oxide ameliorates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

PubMed

Kaushik, Manish Singh; Srivastava, Meenakshi; Srivastava, Alka; Singh, Anumeha; Mishra, Arun Kumar

2016-11-01

In cyanobacterium Anabaena 7120, iron deficiency leads to oxidative stress with unavoidable consequences. Nitric oxide reduces pigment damage and supported the growth of Anabaena 7120 in iron-deficient conditions. Elevation in nitric oxide accumulation and reduced superoxide radical production justified the role of nitric oxide in alleviating oxidative stress in iron deficiency. Increased activities of antioxidative enzymes and higher levels of ROS scavengers (ascorbate, glutathione and thiol) in iron deficiency were also observed in the presence of nitric oxide. Nitric oxide also supported the membrane integrity of Anabaena cells and reduces protein and DNA damage caused by oxidative stress induced by iron deficiency. Results suggested that nitric oxide alleviates the damaging effects of oxidative stress induced by iron deficiency in cyanobacterium Anabaena 7120.

Iron as a catalyst of human low-density lipoprotein oxidation: Critical factors involved in its oxidant properties.

PubMed

Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

2017-05-01

Iron-induced human LDL oxidation, which is relevant to atherosclerosis, has not yet been properly investigated. We addressed such issue using iron(II) and (III) basically in the presence of phosphates, which are present in vivo and influence iron oxidative properties, at pH 4.5 and 7.4, representative, respectively, of the lysosomal and plasma environment. In 10mM phosphate buffered saline (PBS), iron(II) induces substantial LDL oxidation at pH 4.5 at low micromolar concentrations, while at pH 7.4 has low oxidative effects; iron(III) promotes small LDL oxidation only at pH 4.5. In 10mM sodium acetate/NaCl buffer, pH 4.5, iron-induced LDL oxidation is far higher than in PBS, highlighting the relevance of phosphates in the inhibitory modulation of iron-induced LDL oxidation. LDL oxidation is related to iron binding to the protein and lipid moiety of LDL, and requires the presence of iron(II) bound to LDL together with iron(III). Chemical modification of LDL carboxyl groups, which could bind iron especially at pH 4.5, decreases significantly iron binding to LDL and iron-induced LDL oxidation. Hydroxyl radical scavengers are ineffective on iron-induced LDL oxidation, which is inhibited by metal chelation, scavengers of alkoxyl/peroxyl radicals, or removal of LDL lipid hydroperoxides (LOOH). Overall, substantial human LDL oxidation is induced LOOH-dependently by iron(II) at pH 4.5 even in the presence of phosphates, suggesting the occurrence of iron(II)-induced LDL oxidation in vivo within lysosomes, where pH is about 4.5, iron(II) and phosphates coexist, plasma with its antioxidants is absent, and glutathione peroxidase is poorly expressed resulting in LOOH accumulation. Copyright © 2017 Elsevier GmbH. All rights reserved.

Properties of magnetic iron oxides used as materials for wastewater treatment

NASA Astrophysics Data System (ADS)

Matei, E.; Predescu, A.; Vasile, E.; Predescu, A.

2011-07-01

The paper describes the properties of some nanopowders obtained by coprecipitation and used as adsorbent for wastewater treatment. The Fe3O4 and γ-Fe2O3 nanopowders were obtained using iron salts and NaOH as precipitation agents. D-sorbitol was used to prevent the agglomeration between the nanoparticles. The particle size and distribution were detected using a transmission electron microscopy (TEM) and a scanning electron microscope (SEM) equipped with dispersive analyze system in X radiation energy (EDS). The structure of the iron oxide nanoparticles was characterized by X-ray powder diffraction. Thus, the nanoparticles were characterized and compare in terms of particle size and chemical composition and used for adsorption studies in order to removal hexavalent chromium from waste waters.

Planktonic Marine Iron-Oxidizers Drive Iron(III) Mineralization Under Low Oxygen Conditions

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Field, E.; Findlay, A.; MacDonald, D. J.; Chan, C. S. Y.; Kato, S.

2016-02-01

Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive banded iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypotheses was that cyanobacteria produced oxygen that oxidized iron(II) abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron(II)-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron-oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to iron deposits, but there is currently little evidence for planktonic marine iron-oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron-oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 µM O2, <0.2 µM H2S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Instead, cyanobacteria may be providing oxygen for microaerophilic iron(II) oxidation through a symbiotic relationship that promotes oxygen consumption rather than build-up. Our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron(II)-oxidizers were likely important drivers of iron(III) mineralization in ancient oceans.

Selective Inhibition of the Oxidation of Ferrous Iron or Sulfur in Thiobacillus ferrooxidans

PubMed Central

Harahuc, Lesia; Lizama, Hector M.; Suzuki, Isamu

2000-01-01

The oxidation of either ferrous iron or sulfur by Thiobacillus ferrooxidans was selectively inhibited or controlled by various anions, inhibitors, and osmotic pressure. Iron oxidation was more sensitive than sulfur oxidation to inhibition by chloride, phosphate, and nitrate at low concentrations (below 0.1 M) and also to inhibition by azide and cyanide. Sulfur oxidation was more sensitive than iron oxidation to the inhibitory effect of high osmotic pressure. These differences were evident not only between iron oxidation by iron-grown cells and sulfur oxidation by sulfur-grown cells but also between the iron and sulfur oxidation activities of the same iron-grown cells. Growth experiments with ferrous iron or sulfur as an oxidizable substrate confirmed the higher sensitivity of iron oxidation to inhibition by phosphate, chloride, azide, and cyanide. Sulfur oxidation was actually stimulated by 50 mM phosphate or chloride. Leaching of Fe and Zn from pyrite (FeS2) and sphalerite (ZnS) by T. ferrooxidans was differentially affected by phosphate and chloride, which inhibited the solubilization of Fe without significantly affecting the solubilization of Zn. PMID:10698768

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: structure-activity relationship

NASA Astrophysics Data System (ADS)

Guo, Yu; Gu, Dong; Jin, Zhao; Du, Pei-Pei; Si, Rui; Tao, Jing; Xu, Wen-Qian; Huang, Yu-Ying; Senanayake, Sanjaya; Song, Qi-Sheng; Jia, Chun-Jiang; Schüth, Ferdi

2015-03-01

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

DOE PAGES

Guo, Yu; Senanayake, Sanjaya; Gu, Dong; ...

2015-01-12

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO x catalysts with very similar structural characteristics in CO oxidation.« less

Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

PubMed

Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

2015-01-06

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Human ferritin for tumor detection and therapy.

PubMed

Fan, Kelong; Gao, Lizeng; Yan, Xiyun

2013-01-01

Ferritin, a major iron storage protein found in most living organisms, is composed of a 24-subunit protein cage with a hollow interior cavity. Serum ferritin serves as a critical marker to detect total body iron status. However, recent research reveals a number of novel functions of ferritin besides iron storage; for example, a ferritin receptor, transferrin receptor 1 (TfR1), has been identified and serum ferritin levels are found to be elevated in tumors. A particular new finding is that magnetoferritin nanoparticles, biomimetically synthesized using H-chain ferritin to form a 24-subunit cage with an iron oxide core, possess intrinsic dual functionality, the protein shell specifically targeting tumors and the iron oxide core catalyzing peroxidase substrates to produce a color reaction allowing visualization of tumor tissues. Here we attempt to summarize current research on ferritin, particularly newly identified functions related to tumors, in order to address current challenges and highlight future directions. Copyright © 2013 Wiley Periodicals, Inc.

First prokaryotic biodiversity assessment using molecular techniques of an acidic river in Neuquén, Argentina.

PubMed

Urbieta, M Sofía; González Toril, E; Aguilera, A; Giaveno, M Alejandra; Donati, E

2012-07-01

Two acidic hot springs close to the crater of Copahue Volcano (Neuquén, Argentina) are the source of the Río Agrio. The river runs several kilometres before flowing into Caviahue Lake. Along the river, temperature, iron, other metal and proton concentrations decrease gradually with distance downstream. From the source to the lake and depending on the season, pH can rise from 1.0 (or even less) to about 4.0, while temperature values decrease from 70°C to 15°C. Water samples were taken from different stations on the river selected according to their physicochemical parameters. In order to assess prokaryotic biodiversity throughout the water column, different and complementary molecular biology techniques were used, mainly in situ hybridisation and 16S rRNA gene cloning and sequencing. All microorganisms found are typical of acidic environments. Sulphur-oxidizing bacteria like Acidithiobacillus thiooxidans and Acidithiobacillus albertensis were detected in every station. Moderately thermophile iron- and sulphur-oxidizing bacteria like members of Alicyclobacillus and Sulfobacillus genera were also ubiquitous. Strict iron-oxidizing bacteria like Leptospirillum and Ferrimicrobium were present at the source of the river, but disappeared downstream where iron concentrations were much lower. Iron-oxidizing, mesophilic Ferroplasma spp. were the main archaea found. The data presented in this work represent the first molecular assessment of this rare natural acidic environment.

Structural determination of Bi-doped magnetite multifunctional nanoparticles for contrast imaging.

PubMed

Laguna-Marco, M A; Piquer, C; Roca, A G; Boada, R; Andrés-Vergés, M; Veintemillas-Verdaguer, S; Serna, C J; Iadecola, A; Chaboy, J

2014-09-14

To determine with precision how Bi atoms are distributed in Bi-doped iron oxide nanoparticles their structural characterization has been carried out by X-ray absorption spectroscopy (XAS) recorded at the K edge of Fe and at the L3 edge of Bi. The inorganic nanoparticles are nominally hybrid structures integrating an iron oxide core and a bismuth oxide shell. Fe K-edge XAS indicates the formation of a structurally ordered, non-stoichiometric magnetite (Fe3-δO4) phase for all the nanoparticles. The XAS spectra show that, in the samples synthesized by precipitation in aqueous media and laser pyrolysis, the Bi atoms neither enter into the iron oxide spinel lattice nor form any other mixed Bi-Fe oxides. No modification of the local structure around the Fe atoms induced by the Bi atoms is observed at the Fe K edge. In addition, contrary to expectations, our results indicate that the Bi atoms do not form a well-defined Bi oxide structure. The XAS study at the Bi L3 edge indicates that the environment around Bi atoms is highly disordered and only a first oxygen coordination shell is observed. Indefinite [BiO6-x(OH)x] units (isolated or aggregated forming tiny amorphous clusters) bonded through hydroxyl bridges to the nanoparticle, rather than a well defined Bi2O3 shell, surround the nanoparticle. On the other hand, the XAS study indicates that, in the samples synthesized by thermal decomposition, the Bi atoms are embedded in a longer range ordered structure showing the first and second neighbors.

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.

Facile and sustainable synthesis of shaped iron oxide nanoparticles: effect of iron precursor salts on the shapes of iron oxides.

PubMed

Sayed, Farheen N; Polshettiwar, Vivek

2015-05-05

A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner.

Facile and Sustainable Synthesis of Shaped Iron Oxide Nanoparticles: Effect of Iron Precursor Salts on the Shapes of Iron Oxides

PubMed Central

Sayed, Farheen N.; Polshettiwar, Vivek

2015-01-01

A facile and sustainable protocol for synthesis of six different shaped iron oxides is developed. Notably, all the six shapes of iron oxides can be synthesised using exactly same synthetic protocol, by simply changing the precursor iron salts. Several of the synthesised shapes are not reported before. This novel protocol is relatively easy to implement and could contribute to overcome the challenge of obtaining various shaped iron oxides in economical and sustainable manner. PMID:25939969

Review of the Evidence from Epidemiology, Toxicology, and Lung Bioavailability on the Carcinogenicity of Inhaled Iron Oxide Particulates.

PubMed

Pease, Camilla; Rücker, Thomas; Birk, Thomas

2016-03-21

Since the iron-age and throughout the industrial age, humans have been exposed to iron oxides. Here, we review the evidence from epidemiology, toxicology, and lung bioavailability as to whether iron oxides are likely to act as human lung carcinogens. Current evidence suggests that observed lung tumors in rats result from a generic particle overload effect and local inflammation that is rat-specific under the dosing conditions of intratracheal instillation. This mode of action therefore, is not relevant to human exposure. However, there are emerging differences seen in vitro, in cell uptake and cell bioavailability between "bulk" iron oxides and "nano" iron oxides. "Bulk" particulates, as defined here, are those where greater than 70% are >100 nm in diameter. Similarly, "nano" iron oxides are defined in this context as particulates where the majority, usually >95% for pure engineered forms of primary particulates (not agglomerates), fall in the range 1-100 nm in diameter. From the weight of scientific evidence, "bulk" iron oxides are not genotoxic/mutagenic. Recent evidence for "nano" iron oxide is conflicting regarding genotoxic potential, albeit genotoxicity was not observed in an in vivo acute oral dose study, and "nano" iron oxides are considered safe and are being investigated for biomedical uses; there is no specific in vivo genotoxicity study on "nano" iron oxides via inhalation. Some evidence is available that suggests, hypothetically due to the larger surface area of "nano" iron oxide particulates, that toxicity could be exerted via the generation of reactive oxygen species (ROS) in the cell. However, the potential for ROS generation as a basis for explaining rodent tumorigenicity is only apparent if free iron from intracellular "nano" scale iron oxide becomes bioavailable at significant levels inside the cell. This would not be expected from "bulk" iron oxide particulates. Furthermore, human epidemiological evidence from a number of studies suggests that iron oxide is not a human carcinogen, and therefore, based upon the complete weight of evidence, we conclude that "bulk" iron oxides are not human carcinogens.

A Comparative Study of Raw and Metal Oxide Impregnated Carbon Nanotubes for the Adsorption of Hexavalent Chromium from Aqueous Solution

PubMed Central

Qureshi, Muhammad I.; Al-Baghli, Nadhir

2017-01-01

The present study reports the use of raw, iron oxide, and aluminum oxide impregnated carbon nanotubes (CNTs) for the adsorption of hexavalent chromium (Cr(VI)) ions from aqueous solution. The raw CNTs were impregnated with 1% and 10% loadings (weight %) of iron oxide and aluminum oxide nanoparticles using wet impregnation technique. The synthesized materials were characterized using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Batch adsorption experiments were performed to assess the removal efficiency of Cr(VI) ions from water and the effects of pH, contact time, adsorbent dosage, and initial concentration of the Cr(VI) ions were investigated. Results of the study revealed that impregnated CNTs achieved significant increase in the removal efficiency of Cr(VI) ions compared to raw CNTs. In fact, both CNTs impregnated with 10% loading of iron and aluminum oxides were able to remove up to 100% of Cr(VI) ions from aqueous solution. Isotherm studies were carried out using Langmuir and Freundlich isotherm models. Adsorption kinetics of Cr(VI) ions from water was found to be well described by the pseudo-second-order model. The results suggest that metallic oxide impregnated CNTs have very good potential application in the removal of Cr(VI) ions from water resulting in better environmental protection. PMID:28487625

Design and fabrication of N-alkyl-polyethylenimine-stabilized iron oxide nanoclusters for gene delivery.

PubMed

Liu, Gang; Wang, Zhiyong; Lee, Seulki; Ai, Hua; Chen, Xiaoyuan

2012-01-01

With the rapid development of nanotechnology, inorganic magnetic nanoparticles, especially iron oxide nanoparticles (IOs), have emerged as great vehicles for biomedical diagnostic and therapeutic applications. In order to rationally design IO-based gene delivery nanovectors, surface modification is essential and determines the loading and release of the gene of interest. Here we highlight the basic concepts and applications of nonviral gene delivery vehicles based on low molecular weight N-alkyl polyethylenimine-stabilized IOs. The experimental protocols related to these topics are described in this chapter. Copyright © 2012 Elsevier Inc. All rights reserved.

iron phase control during pressure leaching at elevated temperature

NASA Astrophysics Data System (ADS)

Fleuriault, Camille

Iron is a common contaminant encountered in most metal recovery operations, and particularly hydrometallurgical processes. For example, the Hematite Process uses autoclaves to precipitate iron oxide out of the leaching solution, while other metals are solubilized for further hydrometallurgical processing. In some cases, Basic Iron Sulfate (BIS) forms in place of hematite. The presence of BIS is unwanted in the autoclave discharge because it diminishes recovery and causes environmental matters. The focus of this master thesis is on the various iron phases forming during the pressure oxidation of sulfates. Artificial leaching solutions were produced from CuSO4, FeSO4 and H2SO4 in an attempt to recreate the matrix composition and conditions used for copper sulfides autoclaving. The following factors were investigated in order to determine which conditions hinder the formation of BIS: initial free acidity (5 -- 98 g/L), initial copper concentration (12.7 -- 63.5 g/L), initial iron concentration (16.7 -- 30.7 g/L) and initial iron oxidation state. There were three solid species formed in the autoclave: hematite, BIS and hydronium jarosite. The results show that free acid is the main factor influencing the composition of the residue. At an initial concentration of 22.3 g/L iron and no copper added, the upper limit for iron oxide formation is 41 g/L H2SO4. The increase of BIS content in the residue is not gradual and occurs over a change of a few grams per liter around the aforementioned limit. Increasing copper sulfate concentration in the solution hinders the formation of BIS. At 63.5g/L copper, the upper free acidity limit is increased to 61g/L. This effect seems to be related to the buffering action of copper sulfate, decreasing the overall acid concentration and thus extending the stability range of hematite. The effect of varying iron concentration on the precipitate chemistry is unclear. At high iron levels, the only noticeable effect was the inhibition of jarosite. The results were reported within a Cu-Fe-S ternary system and modeled. The modeling confirmed the experimental observations with the exception that increasing iron concentrations seem to promote BIS stability.

Metals and lipid oxidation. Contemporary issues.

PubMed

Schaich, K M

1992-03-01

Lipid oxidation is now recognized to be a critically important reaction in physiological and toxicological processes as well as in food products. This provides compelling reasons to understand what causes lipid oxidation in order to be able to prevent or control the reactions. Redox-active metals are major factors catalyzing lipid oxidation in biological systems. Classical mechanisms of direct electron transfer to double bonds by higher valence metals and of reduction of hydroperoxides by lower valence metals do not always account for patterns of metal catalysis of lipid oxidation in multiphasic or compartmentalized biological systems. To explain why oxidation kinetics, mechanisms, and products in molecular environments which are both chemically and physically complex often do not follow classical patterns predicted by model system studies, increased consideration must be given to five contemporary issues regarding metal catalysis of lipid oxidation: hypervalent non-heme iron or iron-oxygen complexes, heme catalysis mechanism(s), compartmentalization of reactions and lipid phase reactions of metals, effects of metals on product mixes, and factors affecting the mode of metal catalytic action.

Effects of iron-aluminium oxides and organic carbon on aggregate stability of bauxite residues.

PubMed

Zhu, Feng; Li, Yubing; Xue, Shengguo; Hartley, William; Wu, Hao

2016-05-01

In order to successfully establish vegetation on bauxite residue, properties such as aggregate structure and stability require improvement. Spontaneous plant colonization on the deposits in Central China over the last 20 years has revealed that natural processes may improve the physical condition of bauxite residues. Samples from three different stacking ages were selected to determine aggregate formation and stability and its relationship with iron-aluminium oxides and organic carbon. The residue aggregate particles became coarser in both dry and wet sieving processes. The mean weight diameter (MWD) and geometry mean diameter (GMD) increased significantly, and the proportion of aggregate destruction (PAD) decreased. Natural stacking processes could increase aggregate stability and erosion resistant of bauxite residues. Free iron oxides and amorphous aluminium oxides were the major forms in bauxite residues, but there was no significant correlation between the iron-aluminium oxides and aggregate stability. Aromatic-C, alkanes-C, aliphatic-C and alkenes-C were the major functional groups present in the residues. With increasing stacking age, total organic carbon content and aggregate-associated organic carbon both increased. Alkanes-C, aliphatic-C and alkenes-C increased and were mainly distributed in macro-aggregates, whereas aromatic-C was mainly distributed in <0.05-mm aggregates. Organic carbon stability in micro-aggregates was higher than that in macro-aggregates and became more stable. Organic carbon contents in total residues, and within different aggregate sizes, were all negatively correlated with PAD. It indicated that organic materials had a more significant effect on macro-aggregate stability and the effects of iron-aluminium oxides maybe more important for stability of micro-aggregates.

Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

DOEpatents

Shen, Ming-Shing; Yang, Ralph T.

1980-01-01

Lime utilization for sulfurous oxides absorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. It is found that iron oxide present in the spent limestone acts as a catalyst to regenerate the spent limestone in a reducing environment. With only small quantities of iron oxide the calcium can be recycled at a significantly increased rate.

Tuning the oxidative power of free iron-sulfur clusters.

PubMed

Lang, Sandra M; Zhou, Shaodong; Schwarz, Helmut

2017-03-15

The gas-phase reactions between a series of di-iron sulfur clusters Fe 2 S x + (x = 1-3) and the small alkenes C 2 H 4 , C 3 H 6 , and C 4 H 8 have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order Fe 2 S + < Fe 2 S 2 + < Fe 2 S 3 + . In particular, Fe 2 S + and Fe 2 S 2 + only form simple association products, whereas the sulfur-rich Fe 2 S 3 + is able to dehydrogenate propene and 2-butene via desulfurization of the cluster and formation of H 2 S. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of Fe 2 S 3 + that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of Fe 2 S 3 + to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes

PubMed Central

Ntim, Susana Addo; Mitra, Somenath

2011-01-01

This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L−1. The absorption capacity of the composite was 1723 µg g−1 and 189 µg g−1 for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models. PMID:21625394

Chondroitin sulfate-capped super-paramagnetic iron oxide nanoparticles as potential carriers of doxorubicin hydrochloride.

PubMed

Mallick, Neha; Anwar, Mohammed; Asfer, Mohammed; Mehdi, Syed Hassan; Rizvi, Mohammed Moshahid Alam; Panda, Amulya Kumar; Talegaonkar, Sushama; Ahmad, Farhan Jalees

2016-10-20

Chondroitin-4-sulfate (CS), a glycosaminoglycan, was used to prepare CS-capped super-paramagnetic iron oxide nanoparticles, which were further employed for loading a water-soluble chemotherapeutic agent (doxorubicin hydrochloride, DOX). CS-capped SPIONs have potential biomedical application in cancer targeting. The optimized formulation had a hydrodynamic size of 91.2±0.8nm (PDI; 0.228±0.004) and zeta potential of -49.1±1.66mV. DOX was loaded onto the formulation up to 2% (w/w) by physical interaction with CS. TEM showed nano-sized particles having a core-shell structure. XRD confirmed crystal phase of iron oxide. FT-IR conceived the interaction of iron oxide with CS as bidentate chelation and also confirmed DOX loading. Vibration sample magnetometry confirmed super-paramagnetic nature of nanoparticles, with saturation magnetization of 0.238emug(-1). In vitro release profile at pH 7.4 showed that 96.67% of DOX was released within 24h (first order kinetics). MTT assay in MCF7 cells showed significantly higher (p<0.0001) cytotoxicity for DOX in SPIONs than DOX solution (IC50 values 6.294±0.4169 and 11.316±0.1102μgmL(-1), respectively). Copyright © 2016 Elsevier Ltd. All rights reserved.

High manganese concentrations in rocks at Gale crater, Mars

USGS Publications Warehouse

Lanza, Nina L.; Fischer, Woodward W.; Wiens, Roger C.; Grotzinger, John P.; Ollila, Ann M.; Anderson, Ryan B.; Clark, Benton C.; Gellert, Ralf; Mangold, Nicolas; Maurice, Sylvestre; Le Mouélic, Stéphane; Nachon, Marion; Schmidt, Mariek E.; Berger, Jeffrey; Clegg, Samuel M.; Forni, Olivier; Hardgrove, Craig; Melikechi, Noureddine; Newsom, Horton E.; Sautter, Violaine

2014-01-01

The surface of Mars has long been considered a relatively oxidizing environment, an idea supported by the abundance of ferric iron phases observed there. However, compared to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks, it provides a more specific redox indicator of aqueous environments. Observations from the ChemCam instrument on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1–2 orders of magnitude higher than previously observed on Mars, suggesting the presence of an as-yet unidentified manganese-rich phase. These results show that the Martian surface has at some point in time hosted much more highly oxidizing conditions than has previously been recognized.

Geochemical patterns and microbial contribution to iron plaque formation in the rice plant rhizosphere

NASA Astrophysics Data System (ADS)

Maisch, Markus; Murata, Chihiro; Unger, Julia; Kappler, Andreas; Schmidt, Caroline

2015-04-01

Rice is the major food source for more than half of the world population and 80 percent of the worldwide rice cultivation is performed on water logged paddy soils. The establishment of reducing conditions in the soil and across the soil-water interface not only stimulates the microbial production and release of the greenhouse gas methane. These settings also create optimal conditions for microbial iron(III) reduction and therefore saturate the system with reduced ferrous iron. Through the reduction and dissolution of ferric minerals that are characterized by their high surface activity, sorbed nutrients and contaminants (e.g. arsenic) will be mobilized and are thus available for uptake by plants. Rice plants have evolved a strategy to release oxygen from their roots in order to prevent iron toxification in highly ferrous environments. The release of oxygen to the reduced paddy soil causes ferric iron plaque formation on the rice roots and finally increases the sorption capacity for toxic metals. To this date the geochemical and microbiological processes that control the formation of iron plaque are not deciphered. It has been hypothesized that iron(II)-oxidizing bacteria play a potential role in the iron(III) mineral formation along the roots. However, not much is known about the actual processes, mineral products, and geochemical gradients that establish within the rhizosphere. In the present study we have developed a growth set-up that allows the co-cultivation of rice plants and iron(II)-oxidizing bacteria, as well as the visual observation and in situ measurement of geochemical parameters. Oxygen and dissolved iron(II) gradients have been measured using microelectrodes and show geochemical hot spots that offer optimal growth conditions for microaerophilic iron(II) oxidizers. First mineral identification attempts of iron plaque have been performed using Mössbauer spectroscopy and microscopy. The obtained results on mineraology and crystallinity have been compared to mineralogical data from purely biotic (microaerophilic) and abiotic iron mineral formation processes.

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.

Magnetic activated carbon-Fe3O4 nanocomposites--synthesis and applications in the removal of acid yellow dye 17 from water.

PubMed

Ranjithkumar, V; Hazeen, A Nizarul; Thamilselvan, M; Vairam, S

2014-07-01

In this work, synthesis of activated carbon-Fe3O4 composites using activated carbon and iron benzoate/oxalate precursors by simple pyrolytic method and its utility for the removal of acid yellow dye from water are presented. Iron carboxylates held up into the pores of carbon dissociate at their decomposition temperatures form dispersed Fe3O4 nanoparticles in carbon matrix. The composites were characterized by FTIR, PXRD, SEM, TEM, EDX and magnetization measurements. The size of the nano iron oxides are in the range of 21-33 nm formed from iron benzoate precursor and 6-11 nm from iron oxalate precursor. The oxides are magnetic and their saturation magnetization in the range of 0.08-0.16 emu/g and Coercivity (H(c)) 474-600, being lower and higher than that of bare bulk Fe3O4 are due to the nano size of oxides. Composites find application in the removal of acid yellow dye 17 from the synthetic aqueous solution at pH 5. The adsorption data are found to fit well for Langmuir adsorption isotherm. Kinetics data of adsorption of dyes indicate that the adsorption follows pseudo-second order kinetic model.

The transformation of hexabromocyclododecane using zerovalent iron nanoparticle aggregates.

PubMed

Tso, Chih-ping; Shih, Yang-hsin

2014-07-30

Hexabromocyclododecane (HBCD), an emerging contaminant, is a brominated flame retardant that has been widely detected in the environment. In this study, nanoscale zerovalent iron (NZVI) aggregates are firstly used to treat HBCD and its removal under different geochemical conditions is evaluated. HBCD is almost removed from solutions by NZVI, with a kSA of 4.22×10(-3)Lm(-2)min(-1). An increase in the iron dosage and temperature increases the removal rate. The activation energy for the removal of HBCD by NZVI is 30.2kJmol(-1), which suggests that a surface-chemical reaction occurs on NZVI. HBCD is adsorbed on the NZVI surface, where electrons were transferred to HBCD, and consequently forms byproducts with less bromide. Three common groundwater anions decrease the reaction kinetics and efficiency of NZVI. The kobs of HBCD in the presence of anions is in the order: pure water >Cl(-)>NO3(-)≒HCO3(-). The inhibitory effect of these anions may be a result of the possible complexation of anions with the oxidized iron surface. The oxidized sites on NZVI and oxidized species of iron also contribute to the removal of HBCD by adsorption on NZVI from solutions. Copyright © 2014 Elsevier B.V. All rights reserved.

Redox Transformations of Iron at Extremely Low pH: Fundamental and Applied Aspects.

PubMed

Johnson, D Barrie; Kanao, Tadayoshi; Hedrich, Sabrina

2012-01-01

Many different species of acidophilic prokaryotes, widely distributed within the domains Bacteria and Archaea, can catalyze the dissimilatory oxidation of ferrous iron or reduction of ferric iron, or can do both. Microbially mediated cycling of iron in extremely acidic environments (pH < 3) is strongly influenced by the enhanced chemical stability of ferrous iron and far greater solubility of ferric iron under such conditions. Cycling of iron has been demonstrated in vitro using both pure and mixed cultures of acidophiles, and there is considerable evidence that active cycling of iron occurs in acid mine drainage streams, pit lakes, and iron-rich acidic rivers, such as the Rio Tinto. Measurements of specific rates of iron oxidation and reduction by acidophilic microorganisms show that different species vary in their capacities for iron oxido-reduction, and that this is influenced by the electron donor provided and growth conditions used. These measurements, and comparison with corresponding data for oxidation of reduced sulfur compounds, also help explain why ferrous iron is usually used preferentially as an electron donor by acidophiles that can oxidize both iron and sulfur, even though the energy yield from oxidizing iron is much smaller than that available from sulfur oxidation. Iron-oxidizing acidophiles have been used in biomining (a technology that harness their abilities to accelerate the oxidative dissolution of sulfidic minerals and thereby facilitate the extraction of precious and base metals) for several decades. More recently they have also been used to simultaneously remediate iron-contaminated surface and ground waters and produce a useful mineral by-product (schwertmannite). Bioprocessing of oxidized mineral ores using acidophiles that catalyze the reductive dissolution of ferric iron minerals such as goethite has also recently been demonstrated, and new biomining technologies based on this approach are being developed.

Redox Transformations of Iron at Extremely Low pH: Fundamental and Applied Aspects

PubMed Central

Johnson, D. Barrie; Kanao, Tadayoshi; Hedrich, Sabrina

2012-01-01

Many different species of acidophilic prokaryotes, widely distributed within the domains Bacteria and Archaea, can catalyze the dissimilatory oxidation of ferrous iron or reduction of ferric iron, or can do both. Microbially mediated cycling of iron in extremely acidic environments (pH < 3) is strongly influenced by the enhanced chemical stability of ferrous iron and far greater solubility of ferric iron under such conditions. Cycling of iron has been demonstrated in vitro using both pure and mixed cultures of acidophiles, and there is considerable evidence that active cycling of iron occurs in acid mine drainage streams, pit lakes, and iron-rich acidic rivers, such as the Rio Tinto. Measurements of specific rates of iron oxidation and reduction by acidophilic microorganisms show that different species vary in their capacities for iron oxido-reduction, and that this is influenced by the electron donor provided and growth conditions used. These measurements, and comparison with corresponding data for oxidation of reduced sulfur compounds, also help explain why ferrous iron is usually used preferentially as an electron donor by acidophiles that can oxidize both iron and sulfur, even though the energy yield from oxidizing iron is much smaller than that available from sulfur oxidation. Iron-oxidizing acidophiles have been used in biomining (a technology that harness their abilities to accelerate the oxidative dissolution of sulfidic minerals and thereby facilitate the extraction of precious and base metals) for several decades. More recently they have also been used to simultaneously remediate iron-contaminated surface and ground waters and produce a useful mineral by-product (schwertmannite). Bioprocessing of oxidized mineral ores using acidophiles that catalyze the reductive dissolution of ferric iron minerals such as goethite has also recently been demonstrated, and new biomining technologies based on this approach are being developed. PMID:22438853

Electron spin resonance spectroscopy for immunoassay using iron oxide nanoparticles as probe.

PubMed

Jiang, Jia; Tian, Sizhu; Wang, Kun; Wang, Yang; Zang, Shuang; Yu, Aimin; Zhang, Ziwei

2018-02-01

With the help of iron oxide nanoparticles, electron spin resonance spectroscopy (ESR) was applied to immunoassay. Iron oxide nanoparticles were used as the ESR probe in order to achieve an amplification of the signal resulting from the large amount of Fe 3+ ion enclosed in each nanoparticle. Rabbit IgG was used as antigen to test this method. Polyclonal antibody of rabbit IgG was used as antibody to detect the antigen. Iron oxide nanoparticle with a diameter of either 10 or 30 nm was labeled to the antibody, and Fe 3+ in the nanoparticle was probed for ESR signal. The sepharose beads were used as solid phase to which rabbit IgG was conjugated. The nanoparticle-labeled antibody was first added in the sample containing antigen, and the antigen-conjugated sepharose beads were then added into the sample. The nanoparticle-labeled antibody bound to the antigen on sepharose beads was separated from the sample by centrifugation and measured. We found that the detection ranges of the antigen obtained with nanoparticles of different sizes were different because the amount of antibody on nanoparticles of 10 nm was about one order of magnitude higher than that on nanoparticles of 30 nm. When 10 nm nanoparticle was used as probe, the upper limit of detection was 40.00 μg mL -1 , and the analytical sensitivity was 1.81 μg mL -1 . When 30 nm nanoparticle was used, the upper limit of detection was 3.00 μg mL -1 , and the sensitivity was 0.014 and 0.13 μg mL -1 depending on the ratio of nanoparticle to antibody. Graphical abstract Schematic diagram of procedure and ESR spectra.

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD).

PubMed

Pan, Yi-Fong; Chiou, Cary T; Lin, Tsair-Fuh

2010-09-01

PURPOSES AND AIMS: Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water. An industrial-grade diatomite was used as the iron oxide support. The diatomite was first acidified and dried and then coated with iron oxide up to five times. The prepared IOCD samples were characterized for their morphology, composition, elemental content, and crystal properties by various instruments. Experiments of equilibrium and kinetic adsorption of As(V) on IOCD were conducted using 0.1- and 2-L polyethylene bottles, respectively, at different pH and temperatures. Iron oxide (alpha-Fe(2)O(3) hematite) coated onto diatomite greatly improves (by about 30 times) the adsorption of As(V) from water by IOCD as compared to using raw diatomite. This improvement was attributed to increases in both surface affinity and surface area of the IOCD. The surface area of IOCD increased to an optimal value. However, as the IOCD surface area (93 m(2)/g) was only 45% higher than that of raw diatomite (51 m(2)/g), the enhanced As(V) adsorption resulted primarily from the enhanced association of negatively charged As(V) ions with the partial positive surface charge of the iron oxide. The As(V) adsorption decreased when the solution pH was increased from 3.5 to 9.5, as expected from the partial charge interaction between As(V) and IOCD. The adsorption data at pH 5.5 and 7.5 could be well fitted to the Freundlich equation. A moderately high exothermic heat was observed for the As(V) adsorption, with the calculated molar isosteric heat ranging from -4 to -9 kcal/mol. The observed heats fall between those for physical adsorption and chemisorption and are indicative of the formation of a series of ion-pair complexes of As(V) ions with iron oxide surface groups. This study demonstrated that the granular IOCD was successfully developed and employed to remove the As(V) in aqueous solution. The Freundlich isotherm well fitted the equilibrium adsorption data of As(V) onto IOCD, and both the pseudo-second-order model and the pore diffusion model simulated well the adsorption kinetics. Compared to other iron-oxide-based adsorbents reported in the literatures, the adsorption capacity of IOCD is relatively high and its kinetics is fast.

Oxidation resistant alloys, method for producing oxidation resistant alloys

DOEpatents

Dunning, John S.; Alman, David E.

2002-11-05

A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800 C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800 C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700 C. at a low cost

Effects of iron content in Ni-Cr-xFe alloys and immersion time on the oxide films formed in a simulated PWR water environment

NASA Astrophysics Data System (ADS)

Ru, Xiangkun; Lu, Zhanpeng; Chen, Junjie; Han, Guangdong; Zhang, Jinlong; Hu, Pengfei; Liang, Xue

2017-12-01

The iron content in Ni-Cr-xFe (x = 0-9 at.%) alloys strongly affected the properties of oxide films after 978 h of immersion in the simulated PWR primary water environment at 310 °C. Increasing the iron content in the alloys increased the amount of iron-bearing polyhedral spinel oxide particles in the outer oxide layer and increased the local oxidation penetrations into the alloy matrix from the chromium-rich inner oxide layer. The effects of iron content in the alloys on the oxide film properties after 500 h of immersion were less significant than those after 978 h. Iron content increased, and chromium content decreased, in the outer oxide layer with increasing iron content in the alloys. Increasing the immersion time facilitated the formation of the local oxidation penetrations along the matrix/film interface and the nickel-bearing spinel oxides in the outer oxide layer.

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

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

Dubinsky, E.A.; Silver, W.L.; Firestone, M.K.

2009-10-15

We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500 - 5000 mm yr-1) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally dynamic redox conditions make iron-transforming microbial communities central to the belowground carbon cycle in these wet tropical forests. The exceedingly high abundance of iron-reducing bacteria (up to 1.2 x 10{sup 9} cells per gram soil) indicated that they possess extensive metabolic capacity to catalyze the reduction ofmore » iron minerals. In soils from the higher rainfall sites, measured rates of ferric iron reduction could account for up to 44 % of organic carbon oxidation. Iron reducers appeared to compete with methanogens when labile carbon availability was limited. We found large numbers of bacteria that oxidize reduced iron at sites with high rates of iron reduction and large numbers of iron-reducers. the coexistence of large populations of ironreducing and iron-oxidizing bacteria is evidence for rapid iron cycling between its reduced and oxidized states, and suggests that mutualistic interactions among these bacteria ultimately fuel organic carbon oxidation and inhibit CH4 production in these upland tropical forests.« less

A portable Hall magnetometer probe for characterization of magnetic iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Araujo, Jefferson F. D. F.; Costa, Mateus C.; Louro, Sonia R. W.; Bruno, Antonio C.

2017-03-01

We have built a portable Hall magnetometer probe, for measuring magnetic properties of iron oxide nanoparticles, that can be used for bulk materials and liquid samples as well. The magnetometer probe consists of four voltage-programmable commercial Hall sensors and a thin acrylic plate for positioning the sensors. In order to operate, it needs to be attached to a pole of an electromagnet and connected to an AD converter and a computer. It acquires a complete magnetization curve in a couple of minutes and has a magnetic moment sensitivity of 3.5×10-7 Am2. We tested its performance with magnetic nanoparticles containing an iron oxide core and having coating layers with different sizes. The magnetization results obtained were compared with measurements performed on commercial stand-alone magnetometers, and exhibited errors of about ±0.2 Am2/kg (i.e 0.4%) at saturation and below 0.5 Am2/kg (i.e. 10%) at remanence.

Iron oxide nanoparticle-based magnetic resonance method to monitor release kinetics from polymeric particles with high resolution.

PubMed

Chan, Minnie; Schopf, Eric; Sankaranarayanan, Jagadis; Almutairi, Adah

2012-09-18

A new method to precisely monitor rapid release kinetics from polymeric particles using super paramagnetic iron oxide nanoparticles, specifically by measuring spin-spin relaxation time (T(2)), is reported. Previously, we have published the formulation of logic gate particles from an acid-sensitive poly-β-aminoester ketal-2 polymer. Here, a series of poly-β-aminoester ketal-2 polymers with varying hydrophobicities were synthesized and used to formulate particles. We attempted to measure fluorescence of released Nile red to determine whether the structural adjustments could finely tune the release kinetics in the range of minutes to hours; however, this standard technique did not differentiate each release rate of our series. Thus, a new method based on encapsulation of iron oxide nanoparticles was developed, which enabled us to resolve the release kinetics of our particles. Moreover, the kinetics matched the relative hydrophobicity order determined by octanol-water partition coefficients. To the best of our knowledge, this method provides the highest resolution of release kinetics to date.

Iron overload favors the elimination of Leishmania infantum from mouse tissues through interaction with reactive oxygen and nitrogen species.

PubMed

Vale-Costa, Sílvia; Gomes-Pereira, Sandra; Teixeira, Carlos Miguel; Rosa, Gustavo; Rodrigues, Pedro Nuno; Tomás, Ana; Appelberg, Rui; Gomes, Maria Salomé

2013-01-01

Iron plays a central role in host-parasite interactions, since both intervenients need iron for survival and growth, but are sensitive to iron-mediated toxicity. The host's iron overload is often associated with susceptibility to infection. However, it has been previously reported that iron overload prevented the growth of Leishmania major, an agent of cutaneous leishmaniasis, in BALB/c mice. In order to further clarify the impact of iron modulation on the growth of Leishmania in vivo, we studied the effects of iron supplementation or deprivation on the growth of L. infantum, the causative agent of Mediterranean visceral leishmaniasis, in the mouse model. We found that dietary iron deficiency did not affect the protozoan growth, whereas iron overload decreased its replication in the liver and spleen of a susceptible mouse strain. The fact that the iron-induced inhibitory effect could not be seen in mice deficient in NADPH dependent oxidase or nitric oxide synthase 2 suggests that iron eliminates L. infantum in vivo through the interaction with reactive oxygen and nitrogen species. Iron overload did not significantly alter the mouse adaptive immune response against L. infantum. Furthermore, the inhibitory action of iron towards L. infantum was also observed, in a dose dependent manner, in axenic cultures of promastigotes and amastigotes. Importantly, high iron concentrations were needed to achieve such effects. In conclusion, externally added iron synergizes with the host's oxidative mechanisms of defense in eliminating L. infantum from mouse tissues. Additionally, the direct toxicity of iron against Leishmania suggests a potential use of this metal as a therapeutic tool or the further exploration of iron anti-parasitic mechanisms for the design of new drugs.

Iron Overload Favors the Elimination of Leishmania infantum from Mouse Tissues through Interaction with Reactive Oxygen and Nitrogen Species

PubMed Central

Vale-Costa, Sílvia; Gomes-Pereira, Sandra; Teixeira, Carlos Miguel; Rosa, Gustavo; Rodrigues, Pedro Nuno; Tomás, Ana; Appelberg, Rui; Gomes, Maria Salomé

2013-01-01

Iron plays a central role in host-parasite interactions, since both intervenients need iron for survival and growth, but are sensitive to iron-mediated toxicity. The host's iron overload is often associated with susceptibility to infection. However, it has been previously reported that iron overload prevented the growth of Leishmania major, an agent of cutaneous leishmaniasis, in BALB/c mice. In order to further clarify the impact of iron modulation on the growth of Leishmania in vivo, we studied the effects of iron supplementation or deprivation on the growth of L. infantum, the causative agent of Mediterranean visceral leishmaniasis, in the mouse model. We found that dietary iron deficiency did not affect the protozoan growth, whereas iron overload decreased its replication in the liver and spleen of a susceptible mouse strain. The fact that the iron-induced inhibitory effect could not be seen in mice deficient in NADPH dependent oxidase or nitric oxide synthase 2 suggests that iron eliminates L. infantum in vivo through the interaction with reactive oxygen and nitrogen species. Iron overload did not significantly alter the mouse adaptive immune response against L. infantum. Furthermore, the inhibitory action of iron towards L. infantum was also observed, in a dose dependent manner, in axenic cultures of promastigotes and amastigotes. Importantly, high iron concentrations were needed to achieve such effects. In conclusion, externally added iron synergizes with the host's oxidative mechanisms of defense in eliminating L. infantum from mouse tissues. Additionally, the direct toxicity of iron against Leishmania suggests a potential use of this metal as a therapeutic tool or the further exploration of iron anti-parasitic mechanisms for the design of new drugs. PMID:23459556

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

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

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

Oxidation of Fe(II) in rainwater.

PubMed

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

Remote sensing of ferric iron minerals as guides for gold exploration

NASA Technical Reports Server (NTRS)

Taranik, Dan L.; Kruse, Fred A.; Goetz, Alexander F. H.; Atkinson, William W.

1991-01-01

The relationship between the surficial iron mineralogy and economic mineralization is investigated, using data from an airborne imaging spectrometer (the 63-channel Geophysical and Environmental Research Imaging Spectrometer) to map the distribution of iron minerals in the Cripple Creek mining district in Colorado. The airborne image data were coregistered with the field map data for the distribution of iron oxides in the district, in a geographic information computer system, in order to compare their information content. It is shown that the remote imagery was able to uniquely identify the mineral hematite, a mixture of goethite/jarosite, and a mixture of hematite/goethite.

Reduction and Oxidation of the Active Site Iron in Tyrosine Hydroxylase: Kinetics and Specificity†

PubMed Central

Frantom, Patrick A.; Seravalli, Javier; Ragsdale, Stephen W.; Fitzpatrick, Paul F.

2006-01-01

Tyrosine hydroxylase (TyrH) is a pterin-dependent enzyme that catalyzes the hydroxylation of tyrosine to form dihydroxyphenylalanine. The oxidation state of the active site iron atom plays a central role in the regulation of the enzyme. The kinetics of reduction of ferric TyrH by several reductants were determined by anaerobic stopped-flow spectroscopy. Anaerobic rapid freeze–quench EPR confirmed that the change in the near-UV absorbance of TyrH upon adding reductant corresponded to iron reduction. Tetrahydrobiopterin reduces wild-type TyrH following a simple second-order mechanism with a rate constant of 2.8 ± 0.1 mM−1 s−1. 6-Methyltetrahydropterin reduces the ferric enzyme with a second-order rate constant of 6.1 ± 0.1 mM−1 s−1 and exhibits saturation kinetics. No EPR signal for a radical intermediate was detected. Ascorbate, glutathione, and 1,4-benzoquinone all reduce ferric TyrH, but much more slowly than tetrahydrobiopterin, suggesting that the pterin is a physiological reductant. E332A TyrH, which has an elevated Km for tetrahydropterin in the catalytic reaction, is reduced by tetrahydropterins with the same kinetic parameters as those of the wild-type enzyme, suggesting that BH4 does not bind in the catalytic conformation during the reduction. Oxidation of ferrous TyrH by molecular oxygen can be described as a single-step second-order reaction, with a rate constant of 210 mM−1 s−1. S40E TyrH, which mimics the phosphorylated state of the enzyme, has oxidation and reduction kinetics similar to those of the wild-type enzyme, suggesting that phosphorylation does not directly regulate the interconversion of the ferric and ferrous forms. PMID:16475826

PVDF membranes containing hybrid nanoparticles for adsorbing cationic dyes: physical insights and mechanism

NASA Astrophysics Data System (ADS)

Sharma, Maya; Madras, Giridhar; Bose, Suryasarathi

2016-07-01

In this study, Fe (iron) and Ag (silver) based adsorbents were synthesized using solution combustion and in situ reduction techniques. The synthesized adsorbents were comprehensively characterized by different techniques including electron microscopy, BET, XRD, Zeta potential etc. Three chlorinated cationic dyes used were malachite green, methyl violet and pyronin Y. These dyes were adsorbed on various synthesized adsorbents [iron III oxide (Fe2O3)], iron III oxide decorated silver nanoparticles by combustion synthesis technique [Fe2O3-Ag(C)] and iron III oxide decorated silver nanoparticles using in situ reduction, [Fe2O3-Ag (S)]. The isotherm and the adsorption kinetics have been studied systematically. The kinetic data can be explained by the pseudo second order model and the adsorption equilibrium followed Langmuir isotherm. The equilibrium and kinetics results suggest that Fe2O3-Ag(S) nanoparticles showed the maximum adsorption among all the adsorbents. Hence, Polyvinylidene fluoride based membranes containing Fe2O3-Ag(S) nanoparticles were prepared via phase inversion (precipitation immersion using DMF/water) technique. The adsorption kinetics were studied in detail and it was observed that the composite membrane showed synergistic improvement in dye adsorption. Such membranes can be used for water purification.

Response of pore water Al, Fe and S concentrations to waterlogging in a boreal acid sulphate soil.

PubMed

Virtanen, Seija; Simojoki, Asko; Hartikainen, Helinä; Yli-Halla, Markku

2014-07-01

Environmental hazards caused by acid sulphate (AS) soils are of worldwide concern. Among various mitigation measures, waterlogging has mainly been studied in subtropical and tropical conditions. To assess the environmental relevance of waterlogging as a mitigation option in boreal AS soils, we arranged a 2.5-year experiment with monolithic lysimeters to monitor changes in the soil redox potential, pH and the concentrations of aluminium (Al), iron (Fe) and sulphur (S) in pore water in response to low and high groundwater levels in four AS soil horizons. The monoliths consisted of acidic oxidized B horizons and a reduced C horizon containing sulphidic material. Eight lysimeters were cropped (reed canary grass, Phalaris arundinacea) and two were bare without a crop. Waterlogging was conducive to reduction reactions causing a slight rise in pH, a substantial increase in Fe (Fepw) and a decrease in Al (Alpw) in the pore water. The increase in Fepw was decisively higher in the cropped waterlogged lysimeters than in the bare ones, which was attributable to the microbiologically catalysed reductive dissolution of poorly ordered iron oxides and secondary minerals. In contrast to warmer climates, Fepw concentrations remained high throughout the experiment, indicating that the reduction was poised in the iron range, while sulphate was not reduced to sulphide. Therefore, the precipitation of iron sulphide was negligible in the environment with a low pH and abundant with poorly ordered Fe oxides. Increased Fe in pore water counteracts the positive effects of waterlogging, when water is flushed from fields to watercourses, where re-oxidation of Fe causes acidity and oxygen depletion. However, waterlogging prevented further oxidation of sulphidic materials and decreased Alpw to one-tenth of the initial concentrations, and even to one-hundredth of the levels in the low water table lysimeters. Copyright © 2014 Elsevier B.V. All rights reserved.

A Polar Corundum Oxide Displaying Weak Ferromagnetism at Room Temperature

PubMed Central

2012-01-01

Combining long-range magnetic order with polarity in the same structure is a prerequisite for the design of (magnetoelectric) multiferroic materials. There are now several demonstrated strategies to achieve this goal, but retaining magnetic order above room temperature remains a difficult target. Iron oxides in the +3 oxidation state have high magnetic ordering temperatures due to the size of the coupled moments. Here we prepare and characterize ScFeO3 (SFO), which under pressure and in strain-stabilized thin films adopts a polar variant of the corundum structure, one of the archetypal binary oxide structures. Polar corundum ScFeO3 has a weak ferromagnetic ground state below 356 K—this is in contrast to the purely antiferromagnetic ground state adopted by the well-studied ferroelectric BiFeO3. PMID:22280499

Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

In situ preparation of high relaxivity iron oxide nanoparticles by coating with chitosan: A potential MRI contrast agent useful for cell tracking

NASA Astrophysics Data System (ADS)

Tsai, Zei-Tsan; Wang, Jen-Fei; Kuo, Hsiao-Yun; Shen, Chia-Rui; Wang, Jiun-Jie; Yen, Tzu-Chen

2010-01-01

Iron oxide nanocrystals are of considerable interest in nanoscience and nanotechnology because of their nanoscale dimensions, nontoxic nature, and superior magnetic properties. Colloidal solutions of magnetic nanoparticles (ferrofluids) with a high magnetite content are highly desirable for most molecular imaging applications. In this paper, we present a method for in situ coating of superparamagnetic iron oxide (SPIO) with chitosan in order to increase the content of magnetite. Iron chloride salts (Fe 3+ and Fe 2+) were directly coprecipitated inside a porous matrix of chitosan by Co-60 γ-ray irradiation in an aqueous solution of acetic acid. Following sonication, iron oxide nanoparticles were formed inside the chitosan matrix at a pH value of 9.5 and a temperature of 50 °C. The [Fe 3+]:[Fe 2+]:[NH 4OH] molar ratio was 1.6:1:15.8. The final ferrofluid was formed with a pH adjustment to approximately 2.0/3.0, alongside with the addition of mannitol and lactic acid. We subsequently characterized the particle size, the zeta potential, the iron concentration, the magnetic contrast, and the cellular uptake of our ferrofluid. Results showed a z-average diameter of 87.2 nm, a polydispersity index (PDI) of 0.251, a zeta potential of 47.9 mV, and an iron concentration of 10.4 mg Fe/mL. The MRI parameters included an R1 value of 22.0 mM -1 s -1, an R2 value of 202.6 mM -1 s -1, and a R2/R1 ratio of 9.2. An uptake of the ferrofluid by mouse macrophages was observed. Altogether, our data show that Co-60 γ-ray radiation on solid chitosan may improve chitosan coating of iron oxide nanoparticles and tackle its aqueous solubility at pH 7. Additionally, our methodology allowed to obtain a ferrofluid with a higher content of magnetite and a fairly unimodal distribution of monodisperse clusters. Finally, MRI and cell experiments demonstrated the potential usefulness of this product as a potential MRI contrast agent that might be used for cell tracking.

Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration.

PubMed

Aher, Ashish; Papp, Joseph; Colburn, Andrew; Wan, Hongyi; Hatakeyama, Evan; Prakash, Prakhar; Weaver, Ben; Bhattacharyya, Dibakar

2017-11-01

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (Fe x O y nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by Fe x O y functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. Fe x O y functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by Fe x O y functionalized membrane for removal of NA.

Dynamics of CrO 3 –Fe 2 O 3 Catalysts during the High-Temperature Water-Gas Shift Reaction: Molecular Structures and Reactivity

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

Keturakis, Christopher J.; Zhu, Minghui; Gibson, Emma K.

2016-06-13

A series of supported CrO 3/Fe 2O 3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O=) 2Cr 6+O 2 species and a bulk Fe 2O 3 phase containing some Cr 3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe 2O 3 bulk phase becomes Femore » 3O 4 ,and surface dioxo (O=) 2Cr 6+O 2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeO x sites, but some minor reduced surface chromia sites are also retained. The Fe 3–-xCr xO 4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C 16O 2/H 2 → C 18O 2/H 2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect.« less

Biogeochemical Activity of Siderophilic Cyanobacteria: Implications for Paleobiogeochemistry

NASA Technical Reports Server (NTRS)

Brown, Igor I.; Sarkisova, Svetlana A.; Auyeung, Weng S.; Garrison, Dan; Allen, Carlton C.; McKay, David S.

2007-01-01

Understanding the patterns of iron oxidation by cyanobacteria (CB) has tremendous importance for paleobiogeochemistry, since cyanobacteria are presumed to have been involved in the global oxidation of ferrous iron during the Precambrian (Cloud, 1973). B.K. Pierson (1999, 2000) first proposed to study iron deposition in iron-depositing hot springs (ID HS) as a model for Precambrian Fe(2+) oxidation. However, neither the iron-dependent physiology of individual species of CB inhabiting iron-depositing hot springs nor their interactions with minerals enriched with iron have been examined thoroughly. Such study could shed light on ancient iron turnover. Cyanobacterial species isolated from ID HS demonstrate elevated tolerance to colloidal Fe(3+) (= 1 mM), while a concentration of 0.4 mM proved toxic for mesophilic Synechocystis PCC 6803. Isolates from ID HS require 0.4-0.6 mM Fe3+ for maximal growth while the iron requirement for Synechocystis is approximately one order of magnitude lower. We have also demonstrated that thick polysaccharide sheaths around cells of CB isolated from ID HS serve as repositories for precipitated iron. The growth of the mesophilic cyanobacteria Phromidium aa in iron-saturated (0.6 mM) DH medium did not lead to iron precipitation on its filament surfaces. However, a 14.3 fil.2 culture, isolated from an ID HS and incubated under the same conditions, was covered with dense layer of precipitated iron. Our results, taken together with Pierson s data concerning the ability of Fe2+ to stimulate photosynthesis in natural CB mats in ID HS, suggest that CB inhabiting ID HS may constitute a new group of the extremophiles - siderophilic CB. Our recent experiments have revealed for the first time that CB isolates from ID HS are also capable of biodeterioration - the etching of minerals, in particular glasses enriched with Fe, Al, Ti, O, and Si. Thus, Precambrian siderophilic cyanobacteria and their predecessors could have been involved not only in iron deposition but also in the global release of elements. The ability of siderophilic CB to participate in iron turnover make them appropriate candidates for biotechnological processes.

Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

PubMed

de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

2011-11-01

Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Mineralogical, crystallographic and morphological characteristics of natural kaolins from the Ivory Coast (West Africa)

NASA Astrophysics Data System (ADS)

Sei, J.; Morato, F.; Kra, G.; Staunton, S.; Quiquampoix, H.; Jumas, J. C.; Olivier-Fourcade, J.

2006-10-01

Thirteen clay samples from four deposits in the Ivory Coast (West Africa) were studied using X-ray diffraction, thermogravimetric analysis and chemical analysis. Mineralogical, crystallographic and morphological characteristics of these samples are given. Kaolinite is the principal mineral but other minerals are present in small quantities: illite, quartz, anatase and iron oxides (oxides and oxyhydroxides). The crystallographic, morphological and surface characteristics are influenced by the presence of these impurities. In particular, the presence of iron oxides was associated with reduced structural ordering and thermal stability of kaolinite and increased specific surface area. These clays could be used in the ceramics industry to make tiles and bricks, and also in agronomy as supports for chemical fertilizers or for environmental protection by immobilising potentially toxic waste products.

A lithotrophic microbial fuel cell operated with pseudomonads-dominated iron-oxidizing bacteria enriched at the anode

PubMed Central

Nguyen, Thuy Thu; Luong, Tha Thanh Thi; Tran, Phuong Hoang Nguyen; Bui, Ha Thi Viet; Nguyen, Huy Quang; Dinh, Hang Thuy; Kim, Byung Hong; Pham, Hai The

2015-01-01

In this study, we attempted to enrich neutrophilic iron bacteria in a microbial fuel cell (MFC)-type reactor in order to develop a lithotrophic MFC system that can utilize ferrous iron as an inorganic electron donor and operate at neutral pHs. Electrical currents were steadily generated at an average level of 0.6 mA (or 0.024 mA cm–2 of membrane area) in reactors initially inoculated with microbial sources and operated with 20 mM Fe2+ as the sole electron donor and 10 ohm external resistance; whereas in an uninoculated reactor (the control), the average current level only reached 0.2 mA (or 0.008 mA cm–2 of membrane area). In an inoculated MFC, the generation of electrical currents was correlated with increases in cell density of bacteria in the anode suspension and coupled with the oxidation of ferrous iron. Cultivation-based and denaturing gradient gel electrophoresis analyses both show the dominance of some Pseudomonas species in the anode communities of the MFCs. Fluorescent in-situ hybridization results revealed significant increases of neutrophilic iron-oxidizing bacteria in the anode community of an inoculated MFC. The results, altogether, prove the successful development of a lithotrophic MFC system with iron bacteria enriched at its anode and suggest a chemolithotrophic anode reaction involving some Pseudomonas species as key players in such a system. The system potentially offers unique applications, such as accelerated bioremediation or on-site biodetection of iron and/or manganese in water samples. PMID:25712332

Mineral resource of the month: iron oxide pigments

USGS Publications Warehouse

,

2008-01-01

The article discusses iron oxide pigments, which have been used as colorants since human began painting as they resist color change due to sunlight exposure, have good chemical resistance and are stable under normal ambient conditions. Cyprus, Italy and Spain are among the countries that are known for the production of iron oxide pigments. Granular forms of iron oxides and nano-sized materials are cited as developments in the synthetic iron oxide pigment industry which are being used in computer disk drives and nuclear magnetic resonance imaging.

Reactive solute transport in streams: 2. Simulation of a pH modification experiment

USGS Publications Warehouse

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-01-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

Reactive Solute Transport in Streams: 2. Simulation of a pH Modification Experiment

NASA Astrophysics Data System (ADS)

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-02-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

Whey Peptide-Iron Complexes Increase the Oxidative Stability of Oil-in-Water Emulsions in Comparison to Iron Salts.

PubMed

Caetano-Silva, Maria Elisa; Barros Mariutti, Lilian Regina; Bragagnolo, Neura; Bertoldo-Pacheco, Maria Teresa; Netto, Flavia Maria

2018-02-28

Food fortification with iron may favor lipid oxidation in both food matrices and the human body. This study aimed at evaluating the effect of peptide-iron complexation on lipid oxidation catalyzed by iron, using oil-in-water (O/W) emulsions as a model system. The extent of lipid oxidation of emulsions containing iron salts (FeSO 4 or FeCl 2 ) or iron complexes (peptide-iron complexes or ferrous bisglycinate) was evaluated during 7 days, measured as primary (peroxide value) and secondary products (TBARS and volatile compounds). Both salts catalyzed lipid oxidation, leading to peroxide values 2.6- to 4.6-fold higher than the values found for the peptide-iron complexes. The addition of the peptide-iron complexes resulted in the formation of lower amounts of secondary volatiles of lipid oxidation (up to 78-fold) than those of iron salts, possibly due to the antioxidant activity of the peptides and their capacity to keep iron apart from the lipid phase, since the iron atom is coordinated and takes part in a stable structure. The peptide-iron complexes showed potential to reduce the undesirable sensory changes in food products and to decrease the side effects related to free iron and the lipid damage of cell membranes in the organism, due to the lower reactivity of iron in the complexed form.

Iron oxyhydroxide mineralization on microbial extracellular polysaccharides

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

Chan, Clara S.; Fakra, Sirine C.; Edwards, David C.

2010-06-22

Iron biominerals can form in neutral pH microaerophilic environments where microbes both catalyze iron oxidation and create polymers that localize mineral precipitation. In order to classify the microbial polymers that influence FeOOH mineralogy, we studied the organic and mineral components of biominerals using scanning transmission X-ray microscopy (STXM), micro X-ray fluorescence ({mu}XRF) microscopy, and high-resolution transmission electron microscopy (HRTEM). We focused on iron microbial mat samples from a creek and abandoned mine; these samples are dominated by iron oxyhydroxide-coated structures with sheath, stalk, and filament morphologies. In addition, we characterized the mineralized products of an iron-oxidizing, stalk-forming bacterial culture isolatedmore » from the mine. In both natural and cultured samples, microbial polymers were found to be acidic polysaccharides with carboxyl functional groups, strongly spatially correlated with iron oxyhydroxide distribution patterns. Organic fibrils collect FeOOH and control its recrystallization, in some cases resulting in oriented crystals with high aspect ratios. The impact of polymers is particularly pronounced as the materials age. Synthesis experiments designed to mimic the biomineralization processes show that the polysaccharide carboxyl groups bind dissolved iron strongly but release it as mineralization proceeds. Our results suggest that carboxyl groups of acidic polysaccharides are produced by different microorganisms to create a wide range of iron oxyhydroxide biomineral structures. The intimate and potentially long-term association controls the crystal growth, phase, and reactivity of iron oxyhydroxide nanoparticles in natural systems.« less

RGD-conjugated iron oxide magnetic nanoparticles for magnetic resonance imaging contrast enhancement and hyperthermia.

PubMed

Zheng, S W; Huang, M; Hong, R Y; Deng, S M; Cheng, L F; Gao, B; Badami, D

2014-03-01

The purpose of this study was to develop a specific targeting magnetic nanoparticle probe for magnetic resonance imaging and therapy in the form of local hyperthermia. Carboxymethyl dextran-coated ultrasmall superparamagnetic iron oxide nanoparticles with carboxyl groups were coupled to cyclic arginine-glycine-aspartic peptides for integrin α(v)β₃ targeting. The particle size, magnetic properties, heating effect, and stability of the arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide were measured. The arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide demonstrates excellent stability and fast magneto-temperature response. Magnetic resonance imaging signal intensity of Bcap37 cells incubated with arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide was significantly decreased compared with that incubated with plain ultrasmall superparamagnetic iron oxide. The preferential uptake of arginine-glycine-aspartic-ultrasmall superparamagnetic iron oxide by target cells was further confirmed by Prussian blue staining and confocal laser scanning microscopy.

Fabrication and characterization of iron oxide dextran composite layers

NASA Astrophysics Data System (ADS)

Iconaru, S. L.; Predoi, S. A.; Beuran, M.; Ciobanu, C. S.; Trusca, R.; Ghita, R.; Negoi, I.; Teleanu, G.; Turculet, S. C.; Matei, M.; Badea, Monica; Prodan, A. M.

2018-02-01

Super paramagnetic iron oxide nanoparticles such as maghemite have been shown to exhibit antimicrobial properties [1-5]. Moreover, the iron oxide nanoparticles have been proposed as a potential magnetically controllable antimicrobial agent which could be directed to a specific infection [3-5]. The present research has focused on studies of the surface and structure of iron oxide dextran (D-IO) composite layers surface and structure. These composite layers were deposited on Si substrates. The structure of iron oxide dextran composite layers was investigated by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) while the surface morphology was evaluated by Scanning Electron Microscopy (SEM). The structural characterizations of the iron oxide dextran composite layers revealed the basic constituents of both iron and dextran structure. Furthermore, the in vitro evaluation of the antifungal effect of the complex layers, which have been shown revealed to be active against C. albicans cells at distinct intervals of time, is exhibited. Our research came to confirm the fungicidal effect of iron oxide dextran composite layers. Also, our results suggest that iron oxide dextran surface may be used for medical treatment of biofilm associated Candida infections.

When Density Functional Approximations Meet Iron Oxides.

PubMed

Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-Dong

2016-10-11

Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe 2 O 3 , Fe 3 O 4 , and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

Preparation and evaluation of poly(2-hydroxyethyl aspartamide)-hexadecylamine-iron oxide for MR imaging of lymph nodes

PubMed Central

2014-01-01

The purpose of this study was to synthesize biocompatible poly(2-hydroxyethyl aspartamide)–C16-iron oxide (PHEA-C16-iron oxide) nanoparticles and to evaluate their efficacy as a contrast agent for magnetic resonance imaging of lymph nodes. The PHEA-C16-iron oxide nanoparticles were synthesized by coprecipitation method. The core size of the PHEA-C16-iron oxide nanoparticles was about 5 to 7 nm, and the overall size of the nanoparticles was around 20, 60, and 150 nm in aqueous solution. The size of the nanoparticles was controlled by the amount of C16. The 3.0-T MRI signal intensity of a rabbit lymph node was effectively reduced after intravenous administration of PHEA-C16-iron oxide with the size of 20 nm. The in vitro and in vivo toxicity tests revealed the high biocompatibility of PHEA-C16-iron oxide nanoparticles. Therefore, PHEA-C16-iron oxide nanoparticles with 20-nm size can be potentially useful as T2-weighted MR imaging contrast agents for the detection of lymph nodes. PMID:24438671

Nanoparticulate NaA zeolite composites for MRI: Effect of iron oxide content on image contrast

NASA Astrophysics Data System (ADS)

Gharehaghaji, Nahideh; Divband, Baharak; Zareei, Loghman

2018-06-01

In the current study, Fe3O4/NaA nanocomposites with various amounts of Fe3O4 (3.4, 6.8 & 10.2 wt%) were synthesized and characterized to study the effect of nano iron oxide content on the magnetic resonance (MR) image contrast. The cell viability of the nanocomposites was investigated by MTT assay method. T2 values as well as r2 relaxivities were determined with a 1.5 T MRI scanner. The results of the MTT assay confirmed the nanocomposites cytocompatibility up to 6.8% of the iron oxide content. Although the magnetization saturations and susceptibility values of the nanocomposites were increased as a function of the iron oxide content, their relaxivity was decreased from 921.78 mM-1 s-1 for the nanocomposite with the lowest iron oxide content to 380.16 mM-1 s-1 for the highest one. Therefore, Fe3O4/NaA nanocomposite with 3.4% iron oxide content led to the best MR image contrast. Nano iron oxide content and dispersion in the nanocomposites structure have important role in the nanocomposite r2 relaxivity and the MR image contrast. Aggregation of the iron oxide nanoparticles is a limiting factor in using of the high iron oxide content nanocomposites.

Microstructural and microtextural characterization of oxide scale on steel using electron backscatter diffraction.

PubMed

Birosca, S; Dingley, D; Higginson, R L

2004-03-01

High-temperature oxidation of steel has been extensively studied. The microstructure of iron oxides is, however, not well understood because of the difficulty in imaging it using conventional methods, such as optical or electron microscopy. A knowledge of the oxide microstructure and texture is critical in understanding how the oxide film behaves during high-temperature deformation of steels and more importantly how it can be removed following processing. Recently, electron back-scatter diffraction (EBSD) has proved to be a powerful technique for distinguishing the different phases in scales. This technique gives valuable information both on the microstructure and on the orientation relationships between the steel and the scale layers. In the current study EBSD has been used to investigate the microstructure and microtexture of iron oxide layers grown on interstitial free steel at different times and temperatures. Heat treatments have been carried out under normal oxidation conditions in order to relate the results to real steel manufacturing in industry. The composition, morphologies, microstructure and microtexture of selected conditions have been studied using EBSD.

Mössbauer study of the effect of pH on Fe valence in iron-polygalacturonate as a medicine for human anaemia

NASA Astrophysics Data System (ADS)

Kuzmann, E.; Garg, V. K.; de Oliveira, A. C.; Klencsár, Z.; Szentmihályi, K.; Fodor, J.; May, Z.; Homonnay, Z.

2015-02-01

Iron-polygalacturonate complexes have been synthesized from polygalacturonic acid by applying a novel preparation method in order to develop medicine suitable for the effective iron supplementation of the human body in the case of anemia. Since the iron uptake depends on the oxidation state of iron, 57Fe Mössbauer spectroscopy was used to study the occurrence of different valence states in the iron-polygalacturonate complexes prepared under different circumstances. The Mössbauer-spectra indicated the presence of iron both in FeII and FeIII states in the investigated iron-polygalacturonate compounds, the occurrence of which varied with the preparation parameters. A correlation of the relative occurrence of iron valence states with the pH has been found. The relative occurrence of FeIII was found to increase with increasing pH. The knowledge of this correlation can help find optimum preparation conditions of iron-polygalacturonates to cure human anemia.

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to complete. Oxidation by O2 in acidic conditions would be slower. Iron photo-oxidation is thus likely responsible for the formation of jarosite-hematite deposits on Mars, provided that shallow standing water bodies could persist for extended periods of time. The oxygen isotopic composition of lepidocrocite precipitated from the photo-oxidation experiment was measured and it is related to the composition of water by mass-dependent fractionation. The precipitate-fluid 18O/16O isotope fractionation of ∼ + 6 ‰ is consistent with previous determinations of oxygen equilibrium fraction factors between iron oxyhydroxides and water.

Moessbauer Mineralogy on the Moon: The Lunar Regolith

NASA Technical Reports Server (NTRS)

Morris, Richard V.; Korotev, Randy L..; Shelfer, Tad D.; Klingelhoefer, Goestar

1997-01-01

A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations.

Oxidation resistant alloys, method for producing oxidation resistant alloys

DOEpatents

Dunning, John S.; Alman, David E.

2002-11-05

A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800.degree. C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800.degree. C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700.degree. C. at a low cost

DETERMINATION OF THE RATES AND PRODUCTS OF FERROUS IRON OXIDATION IN ARSENIC-CONTAMINATED POND WATER.

EPA Science Inventory

Dissolved ferrous iron and arsenic in the presence of insufficient oxygenated ground water is released into a pond. When the mixing of ferrous iron and oxygenated water within the pond occurs, the ferrous iron is oxidized and precipitated as an iron oxide. Groups of experiments...

The effect of bonding environment on iron isotope fractionation between minerals at high temperature

NASA Astrophysics Data System (ADS)

Sossi, Paolo A.; O'Neill, Hugh St. C.

2017-01-01

Central to understanding the processes that drive stable isotope fractionation in nature is their quantification under controlled experimental conditions. The polyvalent element iron, given its abundance in terrestrial rocks, exerts controls on the structural and chemical properties of minerals and melts. The iron isotope compositions of typical high temperature minerals are, however, poorly constrained and their dependence on intensive (e.g. fO2) and extensive (e.g. compositional) variables is unknown. In this work, experiments involving a reference phase, 2 M FeCl2·4H2O(l), together with an oxide mix corresponding to the bulk composition of the chosen mineral were performed in a piston cylinder in Ag capsules. The oxide mix crystallised in situ at 1073 K and 1 GPa, in equilibrium with the iron chloride, and was held for 72 h. In order to characterise the effect of co-ordination and oxidation state on the isotope composition independently, exclusively Fe2+ minerals were substituted in: VIII-fold almandine, VI-fold ilmenite, fayalite and IV-fold chromite and hercynite. Δ57FeMin-FeCl2 increases in the order VIII < VI < IV, consistent with a decrease in the mean Fe-O bond length. Magnetite, which has mixed VI- and IV-fold co-ordination, has the heaviest Δ57Fe by virtue of 2/3 of its iron being the smaller, ferric ion. The composition of the VIFe2+-bearing minerals is similar to that of the aqueous FeCl2 fluid. To the degree that this represents the speciation of iron in fluids exsolving from magmas, the fractionation between them should be small, unless the iron is hosted in magnetite. By contrast, predominantly Fe2+-bearing mantle garnets should preserve a much lighter δ57Fe than their lower pressure spinel counterparts, a signature that may be reflected in partial melts from these lithologies. As the Fe-O bond lengths in fayalite and ilmenite are comparable, their isotope compositions overlap, suggesting that high Ti mare basalts acquired their heavy isotopic signature from ilmenite that crystallised late during lunar magma ocean solidification.

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

Byong-chul Kim; Sushil Gupta; David French

Iron minerals in coke can catalyze its gasification and may affect coke behavior in the blast furnace. The catalytic behavior of iron depends largely upon the nature of the iron-bearing minerals. To determine the mineralogical changes that iron could undergo in the blast furnace, cokes made from three coals containing iron present in different mineral forms (clays, carbonates, and pyrite) were examined. All coke samples were heat-treated in a horizontal furnace at 1373, 1573, and 1773 K and then gasified with CO{sub 2} at 1173 K in a fixed bed reactor (FBR). Coke mineralogy was characterized using quantitative X-ray diffractionmore » (XRD) analysis of coke mineral matter prepared by low-temperature ashing (LTA) and field emission scanning electron microscopy combined with energy dispersive X-ray analysis (FESEM/EDS). The mineralogy of the three cokes was most notably distinguished by differing proportions of iron-bearing phases. During heat treatment and subsequent gasification, iron-containing minerals transformed to a range of minerals but predominantly iron-silicides and iron oxides, the relative amounts of which varied with heat treatment temperature and gasification conditions. The relationship between initial apparent reaction rate and the amount of catalytic iron minerals - pyrrhotite, metallic iron, and iron oxides - was linear and independent of heat treatment temperature at total catalyst levels below 1 wt %. The study showed that the coke reactivity decreased with increasing temperature of heat treatment due to decreased levels of catalytic iron minerals (largely due to formation of iron silicides) as well as increased ordering of the carbon structure. The study also showed that the importance of catalytic mineral matter in determining reactivity declines as gasification proceeds. 37 refs., 13 figs., 7 tabs.« less

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress.

PubMed

Imam, Mustapha Umar; Zhang, Shenshen; Ma, Jifei; Wang, Hao; Wang, Fudi

2017-06-28

Oxidative stress is a common denominator in the pathogenesis of many chronic diseases. Therefore, antioxidants are often used to protect cells and tissues and reverse oxidative damage. It is well known that iron metabolism underlies the dynamic interplay between oxidative stress and antioxidants in many pathophysiological processes. Both iron deficiency and iron overload can affect redox state, and these conditions can be restored to physiological conditions using iron supplementation and iron chelation, respectively. Similarly, the addition of antioxidants to these treatment regimens has been suggested as a viable therapeutic approach for attenuating tissue damage induced by oxidative stress. Notably, many bioactive plant-derived compounds have been shown to regulate both iron metabolism and redox state, possibly through interactive mechanisms. This review summarizes our current understanding of these mechanisms and discusses compelling preclinical evidence that bioactive plant-derived compounds can be both safe and effective for managing both iron deficiency and iron overload conditions.

Antioxidants Mediate Both Iron Homeostasis and Oxidative Stress

PubMed Central

Zhang, Shenshen; Ma, Jifei; Wang, Hao; Wang, Fudi

2017-01-01

Oxidative stress is a common denominator in the pathogenesis of many chronic diseases. Therefore, antioxidants are often used to protect cells and tissues and reverse oxidative damage. It is well known that iron metabolism underlies the dynamic interplay between oxidative stress and antioxidants in many pathophysiological processes. Both iron deficiency and iron overload can affect redox state, and these conditions can be restored to physiological conditions using iron supplementation and iron chelation, respectively. Similarly, the addition of antioxidants to these treatment regimens has been suggested as a viable therapeutic approach for attenuating tissue damage induced by oxidative stress. Notably, many bioactive plant-derived compounds have been shown to regulate both iron metabolism and redox state, possibly through interactive mechanisms. This review summarizes our current understanding of these mechanisms and discusses compelling preclinical evidence that bioactive plant-derived compounds can be both safe and effective for managing both iron deficiency and iron overload conditions. PMID:28657578

A Silica-Supported Iron Oxide Catalyst Capable of Activating Hydrogen Peroxide at Neutral pH Values

PubMed Central

Pham, Anh Le-Tuan; Lee, Changha; Doyle, Fiona M.; Sedlak, David L.

2009-01-01

Iron oxides catalyze the conversion of hydrogen peroxide (H2O2) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values due to competing reactions that decompose H2O2 without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO4)3, AlCl3 and tetraethyl orthosilicate efficiently catalyzed the decomposition of H2O2 into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H2O2 consumed, that was 10 to 40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50 to 80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H2O2 decomposition. PMID:19943668

Effects of simulated deposition of acid mist and iron ore particulate matter on photosynthesis and the generation of oxidative stress in Schinus terebinthifolius Radii and Sophora tomentosa L.

PubMed

Kuki, Kacilda Naomi; Oliva, Marco Antônio; Pereira, Eduardo Gusmão; Costa, Alan Carlos; Cambraia, José

2008-09-15

Particulate matter is a natural occurrence in the environment, but some industries, such as the iron ore sector, can raise the total amount of particles in the atmosphere. This industry is primarily a source of iron and sulfur dioxide particulates. The effects of the pollutants from the iron ore industries on representatives of restinga vegetation in a Brazilian coastal ecosystem were investigated using physiological and biochemical measures. Two species, Schinus terebinthifolius and Sophora tomentosa, were exposed to simulated deposition of acid mist and iron ore particulate matter in acrylic chambers in a greenhouse. Parameters such as gas exchange, fluorescence emission, chlorophyll content, total iron content, antioxidant enzyme activity and malondialdehyde content were assessed in order to evaluate the responses of the two species. Neither treatment was capable of inducing oxidative stress in S. terebinthifolius. Nevertheless, the deposition of iron ore particulates on this species increased chlorophyll content, the maximum quantum efficiency of photosystem II and the electron transport rate, while iron content was unaltered. On the other hand, S. tomentosa showed a greater sensitivity to the treatments. Plants of S. tomentosa that were exposed to acid mist had a decrease in photosynthesis, while the deposition of iron particulate matter led to an increase in iron content and membrane permeability of the leaves. The activities of antioxidant enzymes, such as catalases and superoxide dismutase, were enhanced by both treatments. The results suggested that the two restinga species use different strategies to overcome the stressful conditions created by the deposition of particulate matter, either solid or wet. It seems that while S. terebinthifolius avoided stress, S. tomentosa used antioxidant enzyme systems to partially neutralize oxidative stress. The findings also point to the potential use of S. tomentosa as a biomarker species under field conditions.

Microbial diversity and iron oxidation at Okuoku-hachikurou Onsen, a Japanese hot spring analog of Precambrian iron formations.

PubMed

Ward, L M; Idei, A; Terajima, S; Kakegawa, T; Fischer, W W; McGlynn, S E

2017-11-01

Banded iron formations (BIFs) are rock deposits common in the Archean and Paleoproterozoic (and regionally Neoproterozoic) sedimentary successions. Multiple hypotheses for their deposition exist, principally invoking the precipitation of iron via the metabolic activities of oxygenic, photoferrotrophic, and/or aerobic iron-oxidizing bacteria. Some isolated environments support chemistry and mineralogy analogous to processes involved in BIF deposition, and their study can aid in untangling the factors that lead to iron precipitation. One such process analog system occurs at Okuoku-hachikurou (OHK) Onsen in Akita Prefecture, Japan. OHK is an iron- and CO 2 -rich, circumneutral hot spring that produces a range of precipitated mineral textures containing fine laminae of aragonite and iron oxides that resemble BIF fabrics. Here, we have performed 16S rRNA gene amplicon sequencing of microbial communities across the range of microenvironments in OHK to describe the microbial diversity present and to gain insight into the cycling of iron, oxygen, and carbon in this ecosystem. These analyses suggest that productivity at OHK is based on aerobic iron-oxidizing Gallionellaceae. In contrast to other BIF analog sites, Cyanobacteria, anoxygenic phototrophs, and iron-reducing micro-organisms are present at only low abundances. These observations support a hypothesis where low growth yields and the high stoichiometry of iron oxidized per carbon fixed by aerobic iron-oxidizing chemoautotrophs like Gallionellaceae result in accumulation of iron oxide phases without stoichiometric buildup of organic matter. This system supports little dissimilatory iron reduction, further setting OHK apart from other process analog sites where iron oxidation is primarily driven by phototrophic organisms. This positions OHK as a study area where the controls on primary productivity in iron-rich environments can be further elucidated. When compared with geological data, the metabolisms and mineralogy at OHK are most similar to specific BIF occurrences deposited after the Great Oxygenation Event, and generally discordant with those that accumulated before it. © 2017 John Wiley & Sons Ltd.

Toxicity assessment and comparison between two types of iron oxide nanoparticles in Mytilus galloprovincialis.

PubMed

Taze, Chrysa; Panetas, Ioannis; Kalogiannis, Stavros; Feidantsis, Konstantinos; Gallios, George P; Kastrinaki, Georgia; Konstandopoulos, Athanasios G; Václavíková, Miroslava; Ivanicova, Lucia; Kaloyianni, Martha

2016-03-01

Nanoparticles (NPs), due to their increased application and production, are being released into the environment with unpredictable impact on the physiology of marine organisms, as well as on entire ecosystems and upcoming effects on human health. The aim of the present study was to evaluate and compare the oxidative responses of the mussel Mytilus galloprovincialis after exposure to iron oxide NPs and to iron oxide NPs incorporated into zeolite for 1, 3 and 7 days. Our results showed that both effectors induced changes on animal physiology by causing oxidative stress in hemocytes of exposed mussels compared to control animals. This was shown by the significant increase in reactive oxygen species (ROS) production, protein carbonylation, lipid peroxidation, ubiquitin conjugates and DNA damage. In addition an increase in prooxidant levels as measured by the prooxidant-antioxidant balance (PAB) assay was observed in exposed mussels' hemolymph. The results show that ROS, DNA damage, protein and lipid oxidation, ubiquitin conjugates and PAB could constitute, after further investigation, reliable biomarkers for the evaluation of pollution or other environmental stressors. In addition, more studies are needed in order to ensure the safety of these NPs on various biomedical applications, since it is critical to design NPs that they meet the demands of application without causing cellular toxicity. Copyright © 2015 Elsevier B.V. All rights reserved.

Graphene oxide coated with porous iron oxide ribbons for 2, 4-Dichlorophenoxyacetic acid (2,4-D) removal.

PubMed

Nethaji, S; Sivasamy, A

2017-04-01

Graphene oxide (GO) was prepared from commercially available graphite powder. Porous iron oxide ribbons were grown on the surface of GO by solvothermal process. The prepared GO-Fe 3 O 4 nanocomposites are characterized by FT-IR, XRD, VSM, SEM, TEM, Raman spectroscopy, surface functionality and zero point charge studies. The morphology of the iron oxide ribbons grown on GO is demonstrated with TEM at various magnifications. The presence of magnetite nanoparticles is evident from XRD peaks and the magnetization value is found to be 37.28emu/g. The ratio of intensity of D-peak to G-peak from Raman spectrum is 0.995. The synthesized Graphene oxide-Fe 3 O 4 nanocomposites (GO-Fe 3 O 4 ) were explored for its surface adsorptive properties by using a model organic compound, 2,4-Dichlorophenoxy acetic acid (2,4-D) from aqueous solution. Batch adsorption studies were performed and the equilibrium data are modelled with Langmuir, Freundlich and Temkin isotherms. The maximum monolayer capacity from Langmuir isotherm is 67.26mg/g. Kinetic studies were also carried out and the studied adsorption process followed pseudo second-order rate equation. Mechanism of the adsorption process is studied by fitting the data with intraparticle diffusion model and Boyd plot. The studied adsorption process is both by film diffusion and intraparticle diffusion. Copyright © 2017 Elsevier Inc. All rights reserved.

Iron, copper, and manganese complexes with in vitro superoxide dismutase and/or catalase activities that keep Saccharomyces cerevisiae cells alive under severe oxidative stress.

PubMed

Ribeiro, Thales P; Fernandes, Christiane; Melo, Karen V; Ferreira, Sarah S; Lessa, Josane A; Franco, Roberto W A; Schenk, Gerhard; Pereira, Marcos D; Horn, Adolfo

2015-03-01

Due to their aerobic lifestyle, eukaryotic organisms have evolved different strategies to overcome oxidative stress. The recruitment of some specific metalloenzymes such as superoxide dismutases (SODs) and catalases (CATs) is of great importance for eliminating harmful reactive oxygen species (hydrogen peroxide and superoxide anion). Using the ligand HPClNOL {1-[bis(pyridin-2-ylmethyl)amino]-3-chloropropan-2-ol}, we have synthesized three coordination compounds containing iron(III), copper(II), and manganese(II) ions, which are also present in the active site of the above-noted metalloenzymes. These compounds were evaluated as SOD and CAT mimetics. The manganese and iron compounds showed both SOD and CAT activities, while copper showed only SOD activity. The copper and manganese in vitro SOD activities are very similar (IC50~0.4 μmol dm(-3)) and about 70-fold higher than those of iron. The manganese compound showed CAT activity higher than that of the iron species. Analyzing their capacity to protect Saccharomyces cerevisiae cells against oxidative stress (H2O2 and the O2(•-) radical), we observed that all compounds act as antioxidants, increasing the resistance of yeast cells mainly due to a reduction of lipid oxidation. Especially for the iron compound, the data indicate complete protection when wild-type cells were exposed to H2O2 or O2(•-) species. Interestingly, these compounds also compensate for both superoxide dismutase and catalase deficiencies; their antioxidant activity is metal ion dependent, in the order iron(III)>copper(II)>manganese(II). The protection mechanism employed by the complexes proved to be independent of the activation of transcription factors (such as Yap1, Hsf1, Msn2/Msn4) and protein synthesis. There is no direct relation between the in vitro and the in vivo antioxidant activities. Copyright © 2014 Elsevier Inc. All rights reserved.

Treatment of antimony mine drainage: challenges and opportunities with special emphasis on mineral adsorption and sulfate reducing bacteria.

PubMed

Li, Yongchao; Hu, Xiaoxian; Ren, Bozhi

2016-01-01

The present article summarizes antimony mine distribution, antimony mine drainage generation and environmental impacts, and critically analyses the remediation approach with special emphasis on iron oxidizing bacteria and sulfate reducing bacteria. Most recent research focuses on readily available low-cost adsorbents, such as minerals, wastes, and biosorbents. It is found that iron oxides prepared by chemical methods present superior adsorption ability for Sb(III) and Sb(V). However, this process is more costly and iron oxide activity can be inhibited by plenty of sulfate in antimony mine drainage. In the presence of sulfate reducing bacteria, sulfate can be reduced to sulfide and form Sb(2)S(3) precipitates. However, dissolved oxygen and lack of nutrient source in antimony mine drainage inhibit sulfate reducing bacteria activity. Biogenetic iron oxide minerals from iron corrosion by iron-oxidizing bacteria may prove promising for antimony adsorption, while the micro-environment generated from iron corrosion by iron oxidizing bacteria may provide better growth conditions for symbiotic sulfate reducing bacteria. Finally, based on biogenetic iron oxide adsorption and sulfate reducing bacteria followed by precipitation, the paper suggests an alternative treatment for antimony mine drainage that deserves exploration.

Neonatal iron supplementation potentiates oxidative stress, energetic dysfunction and neurodegeneration in the R6/2 mouse model of Huntington's disease

PubMed Central

Berggren, Kiersten L.; Chen, Jianfang; Fox, Julia; Miller, Jonathan; Dodds, Lindsay; Dugas, Bryan; Vargas, Liset; Lothian, Amber; McAllum, Erin; Volitakis, Irene; Roberts, Blaine; Bush, Ashley I.; Fox, Jonathan H.

2015-01-01

Huntington’s disease (HD) is a progressive neurodegenerative disorder caused by a CAG repeat expansion that encodes a polyglutamine tract in huntingtin (htt) protein. Dysregulation of brain iron homeostasis, oxidative stress and neurodegeneration are consistent features of the HD phenotype. Therefore, environmental factors that exacerbate oxidative stress and iron dysregulation may potentiate HD. Iron supplementation in the human population is common during infant and adult-life stages. In this study, iron supplementation in neonatal HD mice resulted in deterioration of spontaneous motor running activity, elevated levels of brain lactate and oxidized glutathione consistent with increased energetic dysfunction and oxidative stress, and increased striatal and motor cortical neuronal atrophy, collectively demonstrating potentiation of the disease phenotype. Oxidative stress, energetic, and anatomic markers of degeneration were not affected in wild-type littermate iron-supplemented mice. Further, there was no effect of elevated iron intake on disease outcomes in adult HD mice. We have demonstrated an interaction between the mutant huntingtin gene and iron supplementation in neonatal HD mice. Findings indicate that elevated neonatal iron intake potentiates mouse HD and promotes oxidative stress and energetic dysfunction in brain. Neonatal-infant dietary iron intake level may be an environmental modifier of human HD. PMID:25703232

Photoreductive dissolution of iron oxides trapped in ice and its environmental implications.

PubMed

Kim, Kitae; Choi, Wonyong; Hoffmann, Michael R; Yoon, Ho-Il; Park, Byong-Kwon

2010-06-01

The availability of iron has been thought to be a main limiting factor for the productivity of phytoplankton and related with the uptake of atmospheric CO(2) and algal blooms in fresh and sea waters. In this work, the formation of bioavailable iron (Fe(II)(aq)) from the dissolution of iron oxide particles was investigated in the ice phase under both UV and visible light irradiation. The photoreductive dissolution of iron oxides proceeded slowly in aqueous solution (pH 3.5) but was significantly accelerated in polycrystalline ice, subsequently releasing more bioavailable ferrous iron upon thawing. The enhanced photogeneration of Fe(II)(aq) in ice was confirmed regardless of the type of iron oxides [hematite, maghemite (gamma-Fe(2)O(3)), goethite (alpha-FeOOH)] and the kind of electron donors. The ice-enhanced dissolution of iron oxides was also observed under visible light irradiation, although the dissolution rate was much slower compared with the case of UV radiation. The iron oxide particles and organic electron donors (if any) in ice are concentrated and aggregated in the liquid-like grain boundary region (freeze concentration effect) where protons are also highly concentrated (lower pH). The enhanced photodissolution of iron oxides should occur in this confined boundary region. We hypothesized that electron hopping through the interconnected grain boundaries of iron oxide particles facilitates the separation of photoinduced charge pairs. The outdoor experiments carried out under ambient solar radiation of Ny-Alesund (Svalbard, 78 degrees 55'N) also showed that the generation of dissolved Fe(II)(aq) via photoreductive dissolution is enhanced when iron oxides are trapped in ice. Our results imply that the ice(snow)-covered surfaces and ice-cloud particles containing iron-rich mineral dusts in the polar and cold environments provide a source of bioavailable iron when they thaw.

The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean

PubMed Central

Emerson, David

2016-01-01

Primary productivity in at least a third of the sunlit open ocean is thought to be iron-limited. Primary sources of dissolved iron (dFe) to the ocean are hydrothermal venting, flux from the sediments along continental margins, and airborne dust. This article provides a general review of sources of hydrothermal and sedimentary iron to the ocean, and speculates upon the role that iron-cycling microbes play in controlling iron dynamics from these sources. Special attention is paid to iron-oxidizing bacteria (FeOB) that live by oxidizing iron and producing biogenic iron oxides as waste products. The presence and ubiquity of FeOB both at hydrothermal systems and in sediments is only beginning to be appreciated. The biogenic oxides they produce have unique properties that could contribute significantly to the dynamics of dFe in the ocean. Changes in the physical and chemical characteristics of the ocean due to climate change and ocean acidification will undoubtedly impact the microbial iron cycle. A better understanding of the contemporary role of microbes in the iron cycle will help in predicting how these changes could ultimately influence marine primary productivity. PMID:26779157

The detection of HBV DNA with gold-coated iron oxide nanoparticle gene probes

NASA Astrophysics Data System (ADS)

Xi, Dong; Luo, XiaoPing; Lu, QiangHua; Yao, KaiLun; Liu, ZuLi; Ning, Qin

2008-03-01

Gold-coated iron oxide nanoparticle Hepatitis B virus (HBV) DNA probes were prepared, and their application for HBV DNA measurement was studied. Gold-coated iron oxide nanoparticles were prepared by the citrate reduction of tetra-chloroauric acid in the presence of iron oxide nanoparticles which were added as seeds. With a fluorescence-based method, the maximal surface coverage of hexaethiol 30-mer oligonucleotides and the maximal percentage of hybridization strands on gold-coated iron oxide nanoparticles were (120 ± 8) oligonucleotides per nanoparticle, and (14 ± 2%), respectively, which were comparable with those of (132 ± 10) and (22 ± 3%) in Au nanoparticle groups. Large network aggregates were formed when gold-coated iron oxide nanoparticle HBV DNA gene probe was applied to detect HBV DNA molecules as evidenced by transmission electron microscopy and the high specificity was verified by blot hybridization. Our results further suggested that detecting DNA with iron oxide nanoparticles and magnetic separator was feasible and might be an alternative effective method.

Petrographic and Isotopic Evidence for Siderite Precursors to Iron Oxide Cements

NASA Astrophysics Data System (ADS)

Loope, D.

2015-12-01

The origin of iron oxide mineralization in the Navajo Sandstone on the Colorado Plateau is important because of the different forms of distinct self-organization exhibited by these systems, the potential importance of the cements as geochronometers, and their use as analogs for similar mineralization on other planets. We consider this mineralization to be the product of microbially mediated oxidation of siderite in evolving groundwater systems. Iron oxide grain coatings were dissolved and the iron precipitated as siderite during a reducing phase of diagenesis. Upon invasion by oxidizing waters, iron-oxidizing bacteria colonized the redox interface between siderite-cemented and porous sandstone. Precipitation of iron oxide at this interface generated acid that facilitated further siderite dissolution. One difficulty in testing this hypothesis is that siderite is destroyed by the cm-scale transport of iron during oxidation. There are two lines of evidence that support the presence of a siderite precursor in these systems. 1)Rhombic grains that we interpret to be iron oxide pseudomorphs after siderite occur where in-situ oxidation rather than dissolution of the siderite precursor has occurred. 2) The δ56Fe values of these iron oxide cements are typically negative. We have measured the δ56Fe value of Navajo Sandstone to be 0.2‰; a value in good agreement with previous workers (Chan et al., 2006; Busigny and Dauphas, 2007). Bleaching of the sandstones apparently results in near complete removal of Fe with little change in the δ56Fe values of the bulk sandstone. The δ56Fe values of iron oxide cements have a median value of -0.8‰; similar to the value we obtained from ferroan carbonate (-0.86‰). Iron oxide from samples that comprise largely rhombic grains has similar δ56Fe values (-0.5‰) to those obtained from cements produced by siderite dissolution and subsequent oxidation (-0.4‰). Our interpretation is that siderite precipitated from an aqueous solution in which the δ56Fe value was <0.2‰ yielding siderite with δ56Fe values that ranged upward from -1.4‰. Invasion of the Navajo by oxidizing waters resulted in microbially mediated oxidation of the siderite concretions. The strongly negative values of the Fe oxides result from the near-quantitative oxidation of the siderite in a closed system.

Iron oxides as pedoenvironmental indicators: state of the art, answers and questions (Philippe Duchaufour Medal Lecture)

NASA Astrophysics Data System (ADS)

Torrent, J.

2012-04-01

The colour and magnetic properties of soils largely reflect the content and mineralogy of their iron oxides, which in turn relate to the physical, chemical and biological characteristics of the soil environment. For more than 50 years, soil mineralogists and chemists have collected data for iron oxides in soils formed in widely different environments and tried to understand the complex nature of the different suites and formation pathways for these minerals via laboratory experiments. The discovery of ferrihydrite —the poorly crystalline precursor of most Fe oxides— in 1971, and the recognition of its common presence in soils, raised interest in deciphering the environmental factors that affect its transformation into goethite and hematite, the two most abundant crystalline iron oxides in soil. Field observations were consistent with laboratory experiments in which temperature, water activity, pH, foreign ions and organic matter were found to play a key role in the crystallization of ferrihydrite. Thus, the hematite/(hematite + goethite) ratio increased with increasing temperature and also with the likelihood of seasonal soil drying. Exploiting this ratio as a (pedo)environment indicator is, however, not devoid of problems derived from insufficient knowledge of the interactions between the influential chemical variables, difficulties in quantifying the two minerals and changes brought about by reductive dissolution. Soil formation usually leads to magnetic enhancement as a result of the production of magnetite and/or maghemite, which are ferrimagnetic iron oxides, and, possibly, an ordered ferrimagnetic ferrihydrite, as suggested by recent laboratory experiments. The concentration of pedogenic ferrimagnets as estimated via proxies such as magnetic susceptibility or frequency-dependent magnetic susceptibility has been found to relate to climate variables [particularly (paleo)rainfall] in many studies reported over the last 30 years. However, extracting accurate environmental information from magnetic data is hampered by a still incomplete understanding of (i) the pathways through which pedogenic ferrimagnets are formed, and the chemical and biological factors that affect them; and (ii) the genetic relationships between ferrimagnets and other iron oxides. Competing hypotheses on these issues will be presented and their usefulness for pedoenvironmental interpretations discussed.

Climatic thresholds for pedogenic iron oxides under aerobic conditions: Processes and their significance in paleoclimate reconstruction

NASA Astrophysics Data System (ADS)

Long, Xiaoyong; Ji, Junfeng; Barrón, Vidal; Torrent, José

2016-10-01

Iron oxides are widely distributed across the surface of the Earth as a result of the aerobic weathering of primary Fe-bearing minerals. Pedogenic iron oxides which consist mainly of hematite (Hm), goethite (Gt), maghemite (Mgh), are often concentrated synchronously in aerobic soils under low to moderate rainfall regimes. Magnetic susceptibility (χ) and redness, which respectively reflect the content of Mgh and Hm in soils, are considered reasonable pedogenic and climatic indicators in soil taxonomy and paleorainfall reconstruction. However, under high rainfall regimes, the grain growth of Mgh and transformation to Hm, combined with the prior formation of Gt under conditions of high relative humidity (RH), can result in magnetic reduction and dramatic yellowing of soils and sediments, which explains the existence of rainfall thresholds for Mgh and Hm at a large scale even before the pedogenic environment turns anaerobic. In order to capture the rainfall thresholds for Mgh and Hm occurring under aerobic conditions, we explored a tropical transect across a granitic region where the soil color turned from red to yellow under a wide rainfall range of 900-2200 mm/yr and a corresponding mean annual RH range of 77%-85%. We observed a lower rainfall threshold of ∼1500 mm/yr and a corresponding RH ∼80% for Mgh and Hm along this transect, as well as a higher rainfall threshold of ∼1700 mm/yr and a corresponding RH of ∼81% for Gt and total pedogenic iron oxides (citrate/bicarbonate/dithionite-extractable Fe, Fed). Cross-referencing with comparable studies in temperate and subtropical regions, we noted that the rainfall or RH thresholds for Fed and Hm or Mgh likewise increase with temperature. Moreover, the different thresholds for total and individual iron oxide phase indicates that a negative correlation between chemical weathering intensity and redness or χ in sediment sequences can occur under the prevalent climate regime just between their thresholds. Finally, we developed an integrated model to interpret the sequential formation of rainfall thresholds for different pedogenic iron oxides in soils and sediments with conditions from aerobic to anaerobic.

Polymeric nanocomposites loaded with fluoridated hydroxyapatite Ln3+ (Ln = Eu or Tb)/iron oxide for magnetic targeted cellular imaging

PubMed Central

Pan, Jie; Liu, Wei-Jiao; Hua, Chao; Wang, Li-Li; Wan, Dong; Gong, Jun-Bo

2015-01-01

Objective To fabricate polymeric nanocomposites with excellent photoluminescence, magnetic properties, and stability in aqueous solutions, in order to improve specificity and sensitivity of cellular imaging under a magnetic field. Methods Fluoridated Ln3+-doped HAP (Ln3+-HAP) NPs and iron oxides (IOs) can be encapsulated with biocompatible polymers via a modified solvent exaction/evaporation technique to prepare polymeric nanocomposites with fluoridated Ln3+-HAP/iron oxide. The nanocomposites were characterized for surface morphology, fluorescence spectra, magnetic properties and in vitro cytotoxicity. Magnetic targeted cellular imaging of such nanocomposites was also evaluated with confocal laser scanning microscope using A549 cells with or without magnetic field. Results The fabricated nanocomposites showed good stability and excellent luminescent properties, as well as low in vitro cytotoxicity, indicating that the nanocomposites are suitable for biological applications. Nanocomposites under magnetic field achieved much higher cellular uptake via an energy-dependent pathway than those without magnetic field. Conclusion The nanocomposites fabricated in this study will be a promising tool for magnetic targeted cellular imaging with improved specificity and enhanced selection. PMID:26487962

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

Iron removal on feldspar by using Averrhoa bilimbii as bioleaching agent

NASA Astrophysics Data System (ADS)

Amin, Muhammad; Aji, Bramantyo B.; Supriyatna, Yayat Iman; Bahfie, Fathan

2017-01-01

Investigation of Averrhoa bilimbii as bioleaching agent was carried out. Parameters of leaching duration, acid concentration, and temperature were performed in iron removal process. Feldspar with sized 149 µm was diluted in 30 ml acid solution in order to reduce its iron content. The experimental results showed a good technical feasibility of the process which iron oxide content of feldspar was decreased from 2.24% to 0.29%. The lowest iron concentration remained was obtained after 5 hours of leaching treatment at 60 °C, and concentrated (100 vol%) Averrhoa bilimbii extract as bioleaching agent. SEM characterizations were carried out on the feldspar before and after the leaching treatment. The result shows that there were no significant effect of leaching process on the ore morphology.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis and characterization of dextran-coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Predescu, Andra Mihaela; Matei, Ecaterina; Berbecaru, Andrei Constantin; Pantilimon, Cristian; Drăgan, Claudia; Vidu, Ruxandra; Predescu, Cristian; Kuncser, Victor

2018-03-01

Synthesis and characterization of iron oxide nanoparticles coated with a large molar weight dextran for environmental applications are reported. The first experiments involved the synthesis of iron oxide nanoparticles which were coated with dextran at different concentrations. The synthesis was performed by a co-precipitation technique, while the coating of iron oxide nanoparticles was carried out in solution. The obtained nanoparticles were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectrometry, Fourier transform infrared spectroscopy and superconducting quantum interference device magnetometry. The results demonstrated a successful coating of iron oxide nanoparticles with large molar weight dextran, of which agglomeration tendency depended on the amount of dextran in the coating solution. SEM and TEM observations have shown that the iron oxide nanoparticles are of about 7 nm in size.

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.

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2013 CFR

2013-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2012 CFR

2012-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2014 CFR

2014-04-01

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good manufacturing practice...

Oxidation of nickel-aluminum and iron-aluminum alloys

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

Cathcart, J.V.

1984-01-01

The high-temperature oxidation behavior of several ordered alloys in the Ni-Al and Fe-Al systems is reviewed with special emphasis on Ni/sub 3/Al and NiAl. Ordering influences oxidation through its effect on the activities of the alloy components and by changing the point defect concentration in an alloy. Three categories of Ni-Al alloys are distinguished based on Al content and oxidation behavior. A characteristic feature of the oxidation of high-aluminum Ni-Al and Fe-Al alloys is the formation of voids in the substrate at the oxide-metal interface. The mechanism of void formation and its suppression by minor additions of oxygen-active elements aremore » discussed. A brief description of the effect of pre-oxidation on the reactions of Ni/sub 3/Al-base alloys in SO/sub 2//O/sub 2/ environments is also included.« less

Spatially resolved variations in reflectivity across iron oxide thin films

NASA Astrophysics Data System (ADS)

Kelley, Chris S.; Thompson, Sarah M.; Gilks, Daniel; Sizeland, James; Lari, Leonardo; Lazarov, Vlado K.; Matsuzaki, Kosuke; LeFrançois, Stéphane; Cinque, Gianfelice; Dumas, Paul

2017-11-01

The spin polarising properties of the iron oxide magnetite (Fe3O4) make it attractive for use in spintronic devices, but its sensitivity to compositional and structural variations make it challenging to prepare reliably. Infrared microspectroscopy and modelling are used to determine the spatial variation in the chemical composition of three thin films of iron oxide; one prepared by pulsed laser deposition (PLD), one by molecular beam epitaxy (MBE) deposition of iron whilst simultaneously flowing oxygen into the chamber and one by flowing oxygen only once deposition is complete. The technique is easily able to distinguish between films which contain metallic iron and different iron oxide phases as well as spatial variations in composition across the films. The film grown by post-oxidising iron is spatially uniform but not fully oxidised, the film grown by simultaneously oxidising iron showed spatial variation in oxide composition while the film grown by PLD was spatially uniform magnetite.

Distribution of inorganic species in two Antarctic cryptoendolithic microbial communities

NASA Technical Reports Server (NTRS)

Johnston, C. G.; Vestal, J. R.; Friedmann, E. I. (Principal Investigator)

1989-01-01

Chemical differences were noted between two Antarctic cryptoendolithic (hidden within rock) microenvironments colonized by different microbial communities. Microenvironments dominated by cyanobacteria (BPC) had a higher pH (pH 7-8) than those dominated by lichen (LTL) (pH 4.5-5.5). In order to understand the interactions between the microbiota and the inorganic environment, the inorganic environment was characterized. Water-soluble, carbonate-bound, metal-oxide, organically bound, and residual inorganic species were sequentially extracted from rock samples by chemical means. Each fraction was then quantified using inductively coupled plasma atomic emission spectrometry. BPC contained much more water-soluble and carbonate-bound Ca and Mg than LTL. Metal-oxide species of Al, Fe, and Mn were more abundant in LTL than BPC. Metal oxides appeared to be mobilized (in the order Mn > Fe > Al) from the LTL lichen zone but remained immobile in BPC sandstone. The distribution of K and P bound to metal oxide reflected the distribution of iron oxide in LTL, an indication of the importance of iron in controlling the availability of nutrients in this ecosystem. Metal oxides in turn were likely controlled or influenced by organic matter associated with the lichen community. Despite overall depletion of Fe, Al, and K in the lichen zone, SEM X-ray analysis showed that they were enriched in fungal hyphae. Water-soluble P was present despite the presence of metal oxides, which sequester phosphate. This has biological relevance since P is an essential nutrient.

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper... pyrophosphate. Copper sulfate. Iodine Calcium iodate. Calcium iodobehenate. Cuprous iodide. 3,5-Diiodosalicylic.... Thymol iodide. Iron Iron ammonium citrate. Iron carbonate. Iron chloride. Iron gluconate. Iron oxide...

Carbonaceous fuel combustion with improved desulfurization

DOEpatents

Yang, Ralph T.; Shen, Ming-shing

1980-01-01

Lime utilization for sulfurous oxides adsorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. The iron oxide present in the spent limestone is found to catalyze the regeneration rate of the spent limestone in a reducing environment. Thus both the calcium and iron components may be recycled.

Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst

PubMed Central

Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2015-01-01

Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption. PMID:26517827

Enhancement of Treatment Efficiency of Recalcitrant Wastewater Containing Textile Dyes Using a Newly Developed Iron Zeolite Socony Mobil-5 Heterogeneous Catalyst.

PubMed

Ahmad, Mushtaq; Asghar, Anam; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2015-01-01

Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.

Adsorption and photodegradation of methylene blue by iron oxide impregnated on granular activated carbons in an oxalate solution

NASA Astrophysics Data System (ADS)

Kadirova, Zukhra C.; Katsumata, Ken-ichi; Isobe, Toshihiro; Matsushita, Nobuhiro; Nakajima, Akira; Okada, Kiyoshi

2013-11-01

The photocatalytic adsorbents BAU-OA, BAU-CL and BAU-HA with varying iron oxide content (9-10 mass%) were prepared by heat treatment at 250 °C from commercial activated carbon (BAU) impregnated with iron oxalate, chloride, tris-benzohydroxamate, respectively. The XRD patterns showed amorphous structure in the BAU-CL sample (SBET 50 m2/g) and low crystallinity (as FeOOH and Fe2O3 phases) in the BAU-HA and BAU-OA samples (SBET 4 and 111 m2/g, respectively). The methylene blue adsorption capacities was decreased in order of BAU-OA < BAU-CL < BAU-HA sample and the adsorption followed Langmuir model. The apparent MB photodegradation rate constant (kapp) was increased in same order BAU-HA < BAU-CL < BAU-OA under the standard experimental conditions (initial MB concentrations 0.015-0.025 mM; sample content - 10 mg/l; initial oxalic acid concentration - 0.43 mM; pH 3-4; UV illumination). The process included high efficiency combination of adsorption, heterogeneous and homogeneous catalysis under UV and solar lights illumination without addition of hydrogen peroxide. The detoxification of water sample containing organic dyes was confirmed after combined sorption-photocatalytic treatment.

The effect of carboxylic acids on the oxidation of coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Lengyel, Attila; Tolnai, Gyula; Klencsár, Zoltán; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Herojit Singh, L.; Homonnay, Zoltán; Szalay, Roland; Németh, Péter; Szabolcs, Bálint; Ristic, Mira; Music, Svetozar; Kuzmann, Ernő

2018-05-01

57Fe Mössbauer spectroscopy, XRD, and TEM were used to investigate the effect of mandelic- and salicylic acid coatings on the iron oxide nanoparticles. These two carboxylic acids have similar molecules size and stoichiometry, but different structure and acidity. Significant differences were observed between the Mössbauer spectra of samples coated with mandelic acid and salicylic acid. These results indicate that the occurrence of iron microenvironments in the mandelic- and salicylic acid-coated iron oxide nanoparticles is different. The results can be interpreted in terms of the influence of the acidity of carboxylic acids on the formation, core/shell structure, and oxidation of coated iron oxide nanocomposites.

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.

The redox state of iron in the matrix of CI, CM and metamorphosed CM chondrites by XANES spectroscopy

NASA Astrophysics Data System (ADS)

Beck, P.; De Andrade, V.; Orthous-Daunay, F.-R.; Veronesi, G.; Cotte, M.; Quirico, E.; Schmitt, B.

2012-12-01

Carbonaceous chondrites record the action of water at some point of their petrological history. These meteorites are usually connected to low albedo asteroid, which present visible/near-IR absorption explained by iron related absorption within phyllosilicates and oxides. In order to obtain quantitative insight into the mineralogy of iron-bearing phases, we have measured X-ray absorption near-edge spectroscopy at the iron K-edge of matrix from carbonaceous chondrites. This method enables to constrain the redox state and environment of iron in these meteorites. For this study, we selected seven CM chondrites and the CI Orgueil, expected to span a range of aqueous alteration degrees. Our analysis of the pre-edge features show that the redox state of Orgueil (CI) is dominated by octahedral Fe and that the Fe3+/(Fe3++Fe2+) atomic ratio is above 80%. Full-inversion of the spectra suggests that the iron budget is dominated by iron oxides, with additional contributions from phyllosilicate. In the case of the CM, the iron speciation appears different that in the case of Orgueil. Cronstedtite is identified from the inversion of the spectra, and suggested by the presence of significant amount of tetrahedral Fe3+. Within the CM chondrites, a trend of aqueous alteration appears presents, and which is roughly correlated to the scheme defined by Rubin et al. (2007). This trend is characterized by an increase in the amount of iron oxides. Two shock metamorphosed CM are present in our dataset (PCA 91008, WIS 91600). If WIS 91600 does not appear distinguishable, from the CM trend, in the case of PCA 91008, shock metamorphism did impact the pre-edge intensity and an increased amount of anhydrous silicates is found. Although the matrix was dehydrated, significant amount of Fe3+ is still present, providing a memory of the aqueous alteration.

Cancer Cells with Irons in the Fire

PubMed Central

Bystrom, Laura M.; Rivella, Stefano

2014-01-01

Iron is essential for the growth and proliferation of cells, as well as for many biological processes that are important for the maintenance and survival of the human body. However, excess iron is associated with the development of cancer and other pathological conditions, due in part to the pro-oxidative nature of iron and its damaging effects on DNA. Current studies suggest that iron depletion may be beneficial for patients that have diseases associated with iron overload or other iron metabolism disorders that may increase the risk for cancer. On the other hand, studies suggest that cancer cells are more vulnerable to the effects of iron depletion and oxidative stress in comparison to normal cells. Therefore, cancer patients might benefit from treatments that alter both iron metabolism and oxidative stress. This review highlights the pro-oxidant effects of iron, the relationship between iron and cancer development, the vulnerabilities of iron-dependent cancer phenotype, and how these characteristics may be exploited to prevent or treat cancer. PMID:24835768

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.

Preparation and characterization of 6-mercaptopurine-coated magnetite nanoparticles as a drug delivery system.

PubMed

Dorniani, Dena; Hussein, Mohd Zobir Bin; Kura, Aminu Umar; Fakurazi, Sharida; Shaari, Abdul Halim; Ahmad, Zalinah

2013-01-01

Iron oxide nanoparticles are of considerable interest because of their use in magnetic recording tape, ferrofluid, magnetic resonance imaging, drug delivery, and treatment of cancer. The specific morphology of nanoparticles confers an ability to load, carry, and release different types of drugs. We synthesized superparamagnetic nanoparticles containing pure iron oxide with a cubic inverse spinal structure. Fourier transform infrared spectra confirmed that these Fe3O4 nanoparticles could be successfully coated with active drug, and thermogravimetric and differential thermogravimetric analyses showed that the thermal stability of iron oxide nanoparticles coated with chitosan and 6-mercaptopurine (FCMP) was markedly enhanced. The synthesized Fe3O4 nanoparticles and the FCMP nanocomposite were generally spherical, with an average diameter of 9 nm and 19 nm, respectively. The release of 6-mercaptopurine from the FCMP nanocomposite was found to be sustained and governed by pseudo-second order kinetics. In order to improve drug loading and release behavior, we prepared a novel nanocomposite (FCMP-D), ie, Fe3O4 nanoparticles containing the same amounts of chitosan and 6-mercaptopurine but using a different solvent for the drug. The results for FCMP-D did not demonstrate "burst release" and the maximum percentage release of 6-mercaptopurine from the FCMP-D nanocomposite reached about 97.7% and 55.4% within approximately 2,500 and 6,300 minutes when exposed to pH 4.8 and pH 7.4 solutions, respectively. By MTT assay, the FCMP nanocomposite was shown not to be toxic to a normal mouse fibroblast cell line. Iron oxide coated with chitosan containing 6-mercaptopurine prepared using a coprecipitation method has the potential to be used as a controlled-release formulation. These nanoparticles may serve as an alternative drug delivery system for the treatment of cancer, with the added advantage of sparing healthy surrounding cells and tissue.

Preparation and characterization of 6-mercaptopurine-coated magnetite nanoparticles as a drug delivery system

PubMed Central

Dorniani, Dena; Hussein, Mohd Zobir bin; Kura, Aminu Umar; Fakurazi, Sharida; Shaari, Abdul Halim; Ahmad, Zalinah

2013-01-01

Background Iron oxide nanoparticles are of considerable interest because of their use in magnetic recording tape, ferrofluid, magnetic resonance imaging, drug delivery, and treatment of cancer. The specific morphology of nanoparticles confers an ability to load, carry, and release different types of drugs. Methods and results We synthesized superparamagnetic nanoparticles containing pure iron oxide with a cubic inverse spinal structure. Fourier transform infrared spectra confirmed that these Fe3O4 nanoparticles could be successfully coated with active drug, and thermogravimetric and differential thermogravimetric analyses showed that the thermal stability of iron oxide nanoparticles coated with chitosan and 6-mercaptopurine (FCMP) was markedly enhanced. The synthesized Fe3O4 nanoparticles and the FCMP nanocomposite were generally spherical, with an average diameter of 9 nm and 19 nm, respectively. The release of 6-mercaptopurine from the FCMP nanocomposite was found to be sustained and governed by pseudo-second order kinetics. In order to improve drug loading and release behavior, we prepared a novel nanocomposite (FCMP-D), ie, Fe3O4 nanoparticles containing the same amounts of chitosan and 6-mercaptopurine but using a different solvent for the drug. The results for FCMP-D did not demonstrate “burst release” and the maximum percentage release of 6-mercaptopurine from the FCMP-D nanocomposite reached about 97.7% and 55.4% within approximately 2,500 and 6,300 minutes when exposed to pH 4.8 and pH 7.4 solutions, respectively. By MTT assay, the FCMP nanocomposite was shown not to be toxic to a normal mouse fibroblast cell line. Conclusion Iron oxide coated with chitosan containing 6-mercaptopurine prepared using a coprecipitation method has the potential to be used as a controlled-release formulation. These nanoparticles may serve as an alternative drug delivery system for the treatment of cancer, with the added advantage of sparing healthy surrounding cells and tissue. PMID:24106420

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

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.

Enhanced bioremediation of oil contaminated soil by graded modified Fenton oxidation.

PubMed

Xu, Jinlan; Xin, Lei; Huang, Tinglin; Chang, Kun

2011-01-01

Graded modified Fenton's (MF) oxidation is a strategy in which H2O2 is added intermittently to prevent a sharp temperature increase and undesired soil sterilization at soil circumneutral pH versus adding the same amount of H2O2 continuously. The primary objective of the present study was to investigate whether a mild MF pre-oxidation such as a stepwise addition of H2O2 can prevent sterilization and achieve a maximum degradation of tank oil in soil. Optimization experiments of graded MF oxidation were conducted using citric acid, oxalic acid and SOLV-X as iron chelators under different frequencies of H2O2 addition. The results indicated that the activity order of iron chelates decreased as: citric acid (51%) > SOLV-X (44%) > oxalic acid (9%), and citric acid was found to be an optimized iron chelating agent of graded MF oxidation. Three-time addition of H2O2 was found to be favorable and economical due to decreasing total petroleum hydrocarbon removal from three time addition (51%) to five time addition (59%). Biological experiments were conducted after graded MF oxidation of tank oil completed under optimum conditions mentioned above. After graded oxidation, substantially higher increase (31%) in microbial activity was observed with excessive H2O2 (1470 mmol/L, the mol ratio of H2O2:Fe2+ was 210:1) than that of non-oxidized soil. Removal efficiency of tank oil was up to 93% after four weeks. Especially, the oil fraction (C10-C40) became more biodagradable after graded MF oxidation than its absence. Therefore, graded MF oxidation is a mild pretreatment to achieve an effective bioremediation of oil contaminated soil.

Respiratory interactions of soil bacteria with (semi)conductive iron-oxide minerals.

PubMed

Kato, Souichiro; Nakamura, Ryuhei; Kai, Fumiyoshi; Watanabe, Kazuya; Hashimoto, Kazuhito

2010-12-01

Pure-culture studies have shown that dissimilatory metal-reducing bacteria are able to utilize iron-oxide nanoparticles as electron conduits for reducing distant terminal acceptors; however, the ecological relevance of such energy metabolism is poorly understood. Here, soil microbial communities were grown in electrochemical cells with acetate as the electron donor and electrodes (poised at 0.2 V versus Ag/AgCl) as the electron acceptors in the presence and absence of iron-oxide nanoparticles, and respiratory current generation and community structures were analysed. Irrespective of the iron-oxide species (hematite, magnetite or ferrihydrite), the supplementation with iron-oxide minerals resulted in large increases (over 30-fold) in current, while only a moderate increase (∼10-fold) was observed in the presence of soluble ferric/ferrous irons. During the current generation, insulative ferrihydrite was transformed into semiconductive goethite. Clone-library analyses of 16S rRNA gene fragments PCR-amplified from the soil microbial communities revealed that iron-oxide supplementation facilitated the occurrence of Geobacter species affiliated with subsurface clades 1 and 2. We suggest that subsurface-clade Geobacter species preferentially thrive in soil by utilizing (semi)conductive iron oxides for their respiration. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Fosetyl-Al photo-Fenton degradation and its endogenous catalyst inhibition.

PubMed

Micó, María M; Zapata, Ana; Maldonado, Manuel I; Bacardit, Jordi; Malfeito, Jorge; Sans, Carme

2014-01-30

Interferences from many sources can affect photo-Fenton reaction performance. Among them, catalyst inhibition can be caused by the complexation and/or precipitation of iron species by the organic matter and salts present in the reaction media. This is the case of the oxidation of effluents containing organophosphorous fosetyl-Al. The degradation of this fungicide generates phosphate anions that scavenge iron and hinder Fe(II) availability. Experimental design was applied to artificially enlighten photo-Fenton reaction, in order to evaluate fosetyl-Al degradation. The performed experiments suggested how iron inhibition takes place. The monitoring of photo-Fenton reaction over a mixture of fosetyl-Al with other two pesticides also showed the interferences caused by the presence of the fungicide on other species degradation. Solar empowered photo-Fenton was also essayed for comparison purposes. Artificial and solar light photo-Fenton reactions were revealed as effective treatments for the elimination of tested fungicide. However, the phosphate ions generated during fosetyl oxidation decreased iron availability, what hampered organic matter degradation. Copyright © 2014 Elsevier B.V. All rights reserved.

Evaluation of iron aluminide weld overlays for erosion - corrosion resistant boiler tube coatings in low NO{sub x} boilers

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

DuPont, J.N.; Banovic, S.W.; Marder, A.R.

1996-08-01

Low NOx burners are being installed in many fossil fired power plants in order to comply with new Clean Air Regulations. Due to the operating characteristics of these burners, boiler tube sulfidation corrosion is often enhanced and premature tube failures can occur. Failures due to oxidation and solid particle erosion are also a concern. A program was initiated in early 1996 to evaluate the use of iron aluminide weld overlays for erosion/corrosion protection of boiler tubes in Low NOx boilers. Composite iron/aluminum wires will be used with the Gas Metal Arc Welding (GMAW) process to prepare overlays on boiler tubesmore » steels with aluminum contents from 8 to 16wt%. The weldability of the composite wires will be evaluated as a function of chemical composition and welding parameters. The effect of overlay composition on corrosion (oxidation and sulfidation) and solid particle erosion will also be evaluated. The laboratory studies will be complemented by field exposures of both iron aluminide weld overlays and co-extruded tubing under actual boiler conditions.« less

Effect of iron(III) ion on moso bamboo pyrolysis under microwave irradiation.

PubMed

Dong, Qing; Li, Xiangqian; Wang, Zhaoyu; Bi, Yanhong; Yang, Rongling; Zhang, Jinfeng; Luo, Hongzhen; Niu, Miaomiao; Qi, Bo; Lu, Chen

2017-11-01

The effect of iron(III) ion on microwave pyrolysis of moso bamboo was investigated. Hydrofluoric acid washing was used as a pilot process to demineralize moso bamboo in order to eliminate the influences of the other inorganics contained in moso bamboo itself. The results indicated that the addition of iron(III) ion increased the maximal reaction temperatures under microwave condition dependent on the amount of the added iron(III) ion. The production of the non-condensable gases was promoted by the addition of iron(III) ion mainly at the expense of liquid products. Iron(III) ion exhibited the positive effect for syngas production and inhibited the formation of CO 2 and CH 4 . The formation of Fe 2 O 3 and Fe 3 O 4 was found during microwave pyrolysis and the mechanism of the two metallic oxides formation was described in this work. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mineralogy and crystal chemistry of iron in the Timan bauxite and products of their technological processing

NASA Astrophysics Data System (ADS)

Kotova, O.; Silaev, V.; Lutoev, V.; Vakhrushev, A.

2016-04-01

Mineralogical and geochemical features of two series of samples of typical bauxites from two deposits of Middle Timan mining area (Vezhayu-Vorykva and Svetlinskoe) were studied. The phase composition of ferrous bauxites generally is boehmite, hematite, ultradisperse low-ordered goethite and berthierine. In a boehmite and kaolinite structural impurity of iron to 10%, and in the iron oxidehydroxides aluminum impurity is revealed. On iron content bauxites are subdivided into three mineral types for which quantitative data on valence states of ions of iron and proportions of their distribution last on nonequivalent structural positions in hematite, goethite and berthierine are obtained. Noble metals (Ag, Au, Ir, Rh, Pd) concentrating in bauxites are revealed for the first time. Obtained data can lead to decrease of power consumption during aluminum production and high quality ceramics, to provide production of valuable iron oxide, and also to minimize the ecological harm from accumulation of bauxite wastes.

Respiratory enzymes of Thiobacillus ferrooxidans. Kinetic properties of an acid-stable iron:rusticyanin oxidoreductase.

PubMed

Blake, R C; Shute, E A

1994-08-09

Rusticyanin is an acid-stable, soluble blue copper protein found in abundance in the periplasmic space of Thiobacillus ferrooxidans, an acidophilic bacterium capable of growing autotrophically on soluble ferrous sulfate. An acid-stable iron:rusticyanin oxidoreductase activity was partially purified from cell-free extracts of T. ferrooxidans. The enzyme-catalyzed, iron-dependent reduction of the rusticyanin exhibited three kinetic properties characteristic of aerobic iron oxidation by whole cells. (i) A survey of 14 different anions indicated that catalysis by the oxidoreductase occurred only in the presence of sulfate or selenate, an anion specificity identical to that of whole cells. (ii) Saturation with both sulfatoiron(II) and the catalyst produced a concentration-independent rate constant of 3 s-1 for the reduction of the rusticyanin, which is an electron transfer reaction sufficiently rapid to account for the flux of electrons through the iron respiratory chain. (iii) Values for the enzyme-catalyzed pseudo-first-order rate constants for the reduction of the rusticyanin showed a hyperbolic dependence on the concentration of sulfatoiron(II) with a half-maximal effect at 300 microM, a value similar to the apparent KM for iron shown by whole cells. On the basis of these favorable comparisons between the behavior patterns of isolated biomolecules and those of whole cells, this iron:rusticyanin oxidoreductase is postulated to be the primary cellular oxidant of ferrous ions in the iron respiratory electron transport chain of T. ferrooxidans.

Magnetic Characterization of Iron Oxide Nanoparticles for Biomedical Applications.

PubMed

Maldonado-Camargo, Lorena; Unni, Mythreyi; Rinaldi, Carlos

2017-01-01

Iron oxide nanoparticles are of interest in a wide range of biomedical applications due to their response to applied magnetic fields and their unique magnetic properties. Magnetization measurements in constant and time-varying magnetic field are often carried out to quantify key properties of iron oxide nanoparticles. This chapter describes the importance of thorough magnetic characterization of iron oxide nanoparticles intended for use in biomedical applications. A basic introduction to relevant magnetic properties of iron oxide nanoparticles is given, followed by protocols and conditions used for measurement of magnetic properties, along with examples of data obtained from each measurement, and methods of data analysis.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1988-05-17

Apparatus is described for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom. 2 figs.

Steel refining with an electrochemical cell

DOEpatents

Blander, M.; Cook, G.M.

1985-05-21

Disclosed is an apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Steel refining with an electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1988-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contact with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Refractory lining for electrochemical cell

DOEpatents

Blander, Milton; Cook, Glenn M.

1987-01-01

Apparatus for processing a metallic fluid containing iron oxide, container for a molten metal including an electrically conductive refractory disposed for contact with the molten metal which contains iron oxide, an electrolyte in the form of a basic slag on top of the molten metal, an electrode in the container in contcat with the slag electrically separated from the refractory, and means for establishing a voltage across the refractory and the electrode to reduce iron oxide to iron at the surface of the refractory in contact with the iron oxide containing fluid. A process is disclosed for refining an iron product containing not more than about 10% by weight oxygen and not more than about 10% by weight sulfur, comprising providing an electrolyte of a slag containing one or more of calcium oxide, magnesium oxide, silica or alumina, providing a cathode of the iron product in contact with the electrolyte, providing an anode in contact with the electrolyte electrically separated from the cathode, and operating an electrochemical cell formed by the anode, the cathode and the electrolyte to separate oxygen or sulfur present in the iron product therefrom.

Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

NASA Astrophysics Data System (ADS)

Andre, B. J.; Rajaram, H.; Silverstein, J.

2010-12-01

Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction diffusion model at the scale of a single rock is developed incorporating the proposed kinetic rate expressions. Simulations of initiation, washout and AMD flows are discussed to gain a better understanding of the role of porosity, effective diffusivity and reactive surface area in generating AMD. Simulations indicate that flow boundary conditions control generation of acid rock drainage as porosity increases.

Oxidative stress-induced iron signaling is responsible for peroxide-dependent oxidation of dichlorodihydrofluorescein in endothelial cells: role of transferrin receptor-dependent iron uptake in apoptosis.

PubMed

Tampo, Yoshiko; Kotamraju, Srigiridhar; Chitambar, Christopher R; Kalivendi, Shasi V; Keszler, Agnes; Joseph, Joy; Kalyanaraman, B

2003-01-10

Dichlorodihydrofluorescein (DCFH) is one of the most frequently used probes for detecting intracellular oxidative stress. In this study, we report that H2O2-dependent intracellular oxidation of DCFH to a green fluorescent product, 2',7'-dichlorofluorescein (DCF), required the uptake of extracellular iron transported through a transferrin receptor (TfR) in endothelial cells. H2O2-induced DCF fluorescence was inhibited by the monoclonal IgA-class anti-TfR antibody (42/6) that blocked TfR endocytosis and the iron uptake. H2O2-mediated inactivation of cytosolic aconitase was responsible for activation of iron regulatory protein-1 and increased expression of TfR, resulting in an increased iron uptake into endothelial cells. H2O2-mediated caspase-3 proteolytic activation was inhibited by anti-TfR antibody. Similar results were obtained in the presence of a lipid hydroperoxide. We conclude that hydroperoxide-induced DCFH oxidation and endothelial cell apoptosis required the uptake of extracellular iron by the TfR-dependent iron transport mechanism and that the peroxide-induced iron signaling, in general, has broader implications in oxidative vascular biology.

Oxidative stability of a heme iron-fortified bakery product: Effectiveness of ascorbyl palmitate and co-spray-drying of heme iron with calcium caseinate.

PubMed

Alemán, Mercedes; Bou, Ricard; Tres, Alba; Polo, Javier; Codony, Rafael; Guardiola, Francesc

2016-04-01

Fortification of food products with iron is a common strategy to prevent or overcome iron deficiency. However, any form of iron is a pro-oxidant and its addition will cause off-flavours and reduce a product's shelf life. A highly bioavailable heme iron ingredient was selected to fortify a chocolate cream used to fill sandwich-type cookies. Two different strategies were assessed for avoiding the heme iron catalytic effect on lipid oxidation: ascorbyl palmitate addition and co-spray-drying of heme iron with calcium caseinate. Oxidation development and sensory acceptability were monitored in the cookies over one-year of storage at room temperature in the dark. The addition of ascorbyl palmitate provided protection against oxidation and loss of tocopherols and tocotrienols during the preparation of cookies. In general, ascorbyl palmitate, either alone or in combination with the co-spray-dried heme iron, prevented primary oxidation and hexanal formation during storage. The combination of both strategies resulted in cookies that were acceptable from a sensory point of view after 1year of storage. Copyright © 2015 Elsevier Ltd. All rights reserved.

Colour and toxic characteristics of metakaolinite–hematite pigment for integrally coloured concrete, prepared from iron oxide recovered from a water treatment plant of an abandoned coal mine

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

Sadasivam, Sivachidambaram, E-mail: sadasivams@cardiff.ac.uk; Thomas, Hywel Rhys

A metakaolinite-hematite (KH) red pigment was prepared using an ocherous iron oxide sludge recovered from a water treatment plant of an abandoned coal mine. The KH pigment was prepared by heating the kaolinite and the iron oxide sludge at kaolinite's dehydroxylation temperature. Both the raw sludge and the KH specimen were characterised for their colour properties and toxic characteristics. The KH specimen could serve as a pigment for integrally coloured concrete and offers a potential use for the large volumes of the iron oxide sludge collected from mine water treatment plants. - Graphical abstract: A kaolinite based red pigment wasmore » prepared using an ocherous iron oxide sludge recovered from an abandoned coal mine water treatment plant. Display Omitted - Highlights: • A red pigment was prepared by heating a kaolinite and an iron oxide sludge. • The iron oxide and the pigment were characterised for their colour properties. • The red pigment can be a potential element for integrally coloured concrete.« less

Iron Oxide Silica Derived from Sol-Gel Synthesis

PubMed Central

Darmawan, Adi; Smart, Simon; Julbe, Anne; Diniz da Costa, João Carlos

2011-01-01

In this work we investigate the effect of iron oxide embedded in silica matrices as a function of Fe/Si molar ratio and sol pH. To achieve homogeneous dispersion of iron oxide particles, iron nitrate nonahydrate was dissolved in hydrogen peroxide and was mixed with tetraethyl orthosilicate and ethanol in a sol-gel synthesis method. Increasing the calcination temperature led to a reduction in surface area, although the average pore radius remained almost constant at about 10 Å, independent of the Fe/Si molar ratio or sol pH. Hence, the densification of the matrix was accompanied by similar reduction in pore volume. However, calcination at 700 °C resulted in samples with similar surface area though the iron oxide content increased from 5% to 50% Fe/Si molar ratio. As metal oxide particles have lower surface area than polymeric silica structures, these results strongly suggest that the iron oxides opposed the silica structure collapse. The effect of sol pH was found to be less significant than the Fe/Si molar ratio in the formation of molecular sieve structures derived from iron oxide silica. PMID:28879999

Oxidation-Induced Degradable Nanogels for Iron Chelation

NASA Astrophysics Data System (ADS)

Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

2016-02-01

Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells.

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.

Oxidation-Induced Degradable Nanogels for Iron Chelation

PubMed Central

Liu, Zhi; Wang, Yan; Purro, Max; Xiong, May P.

2016-01-01

Iron overload can increase cellular oxidative stress levels due to formation of reactive oxygen species (ROS); untreated, it can be extremely destructive to organs and fatal to patients. Since elevated oxidative stress levels are inherent to the condition in such patients, oxidation-induced degradable nanogels for iron chelation were rationally designed by simultaneously polymerizing oxidation-sensitive host-guest crosslinkers between β-cyclodextrin (β-CD) and ferrocene (Fc) and iron chelating moieties composed of deferoxamine (DFO) into the final gel scaffold in reverse emulsion reaction chambers. UV-Vis absorption and atomic absorption spectroscopy (AAS) was used to verify iron chelating capability of nanogels. These materials can degrade into smaller chelating fragments at rates proportional to the level of oxidative stress present. Conjugating DFO reduces the cytotoxicity of the chelator in the macrophage cells. Importantly, the nanogel can effectively reduce cellular ferritin expression in iron overloaded cells and regulate intracellular iron levels at the same time, which is important for maintaining a homeostatic level of this critical metal in cells. PMID:26868174

Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Bacterial Oxidation of Iron in Olivine: Implications for the Subsurface Biosphere, Global Chemical Cycles, and Life on Mars

NASA Astrophysics Data System (ADS)

Fisk, M. R.; Popa, R.; Smith, A. R.; Popa, R.; Boone, J.

2011-12-01

We isolated 21 species of bacteria from subseafloor and terrestrial basalt environments and which thrive on olivine at neutral pH. Cell numbers increase four to five orders of magnitude over three weeks in media where the only metabolic energy comes from the oxidation of Fe(II) in olivine. The subseafloor bacteria were isolated from a borehole on the flank of Juan de Fuca Ridge in the northeast Pacific basin where the temperature ranged from 4 up to 64 °C over four years. Terrestrial isolates originated from the basalt-ice boundary in a lava tube on the flank of Newberry Caldera in the Cascades of Oregon. The borehole water was either seawater or seawater plus subseafloor formation water and the lava tube ice was frozen meteoric or ground water. Although microorganisms capable of oxidizing iron for growth are known, microbes that oxidize iron from silicate minerals at neutral pH have not previously been cultured. The 21 species in this study are the first neutrophilic, iron-oxidizing bacteria (nFeOB) to be isolated and cultured that grow on olivine. These nFeOB are primary producers and we believe that they are a widespread component of the subsurface biosphere. In addition to their ability use iron from olivine, these microbes assimilate carbon from bicarbonate in solution and can grow when oxygen pressures are low. They also use nitrate as an alternative electron acceptor to oxygen in anaerobiosis. Since basalt is the most common rock in the Earth's crust and iron is the fourth most abundant element in the crust, we believe nFeOB are likely to be a significant portion of the subsurface biosphere. They are likely to affect, and perhaps in some environments control, the weathering rate of olivine and possibly of pyroxene and basalt glass. Olivine is a component of Mars's surface and it is present on other rocky bodies in the solar system. The ability of these bacteria to use Fe(II) from olivine, to assimilate carbon, to grow at low temperature, and to use low levels of oxygen and nitrate as oxidants would allow them to survive below the surface of Mars. These cultured organisms, which are the first known to oxidize iron from olivine at neutral pH, may be a major component of the subsurface biosphere, may affect global chemical cycles of elements in basalt, and could potentially, live in the Martian subsurface.

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

PubMed

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

PubMed

Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

2013-08-19

Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

Pilot scale application of nanosized iron oxides as electron acceptors for bioremediation

NASA Astrophysics Data System (ADS)

Bosch, Julian; Fritzsche, Andreas; Frank-Fahle, Beatrice; Lüders, Tilmann; Höss, Sebastian; Eisenmann, Heinrich; Held, Thomas; Totsche, Kai U.; Meckenstock, Rainer U.

2014-05-01

Microbial reduction of ferric iron is a major biogeochemical process in groundwater aquifer ecosystems and often associated with the degradation of organic contaminants, as bacteria couple iron reduction to the oxidation reduced carbon like e.g. BTEX. Yet in general the low bioavailability of natural iron oxides limits microbial reduction rates. However, nanosized iron oxides have an unequally enhanced bioavailability and reactivity compared to their respective bulk, macro-sized, and more crystalline materials. At the same time, nanosized iron oxides can be produced in stable colloidal suspensions, permitting efficient injections into contaminated aquifers. We examined the reactivity of nanosized synthetic colloidal iron oxides in microbial iron reduction. Application of colloidal nanoparticles led to a strong and sustainable enhancement of microbial reaction rates in batch experiments and sediment columns. Toluene oxidation was increased five-fold as compared to bulk, non-colloidal ferrihydrite as electron acceptor. Furthermore, we developed a unique approach for custom-tailoring the subsurface mobility of these particles after being injected into a contaminant plume. In a field pilot application, we injected 18 m3 of an iron oxide nanoparticle solution into a BTEX contaminated aquifer with a maximum excess pressure as low as 0.2 bar. The applied suspension showed a superior subsurface mobility, creating a reactive zone of 4 m height (corresponding to the height of the confined aquifer) and 6 m in diameter. Subsequent monitoring of BTEX, microbial BTEX degradation metabolites, ferrous iron generation, stable isotopes fractionation, microbial populations, and methanogenesis demonstrated the strong impact of our approach. Mathematic processed X-ray diffractograms and FTIR spectra provided a semi-quantitatively estimate of the long-term fate of the iron oxide colloids in the aquifer. Potential environmental risks of the injection itself were monitored with ecotoxicological investigations. Our data suggest that the injection of ferric iron nanoparticles as electron acceptors into contaminated aquifers for the enhancement of microbial contaminant degradation might develop into a novel bioremediation strategy.

Stabilization and functionalization of iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Amstad, Esther; Textor, Marcus; Reimhult, Erik

2011-07-01

Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given.Superparamagnetic iron oxide nanoparticles (NPs) are used in a rapidly expanding number of research and practical applications in the biomedical field, including magnetic cell labeling separation and tracking, for therapeutic purposes in hyperthermia and drug delivery, and for diagnostic purposes, e.g., as contrast agents for magnetic resonance imaging. These applications require good NP stability at physiological conditions, close control over NP size and controlled surface presentation of functionalities. This review is focused on different aspects of the stability of superparamagnetic iron oxide NPs, from its practical definition to its implementation by molecular design of the dispersant shell around the iron oxide core and further on to its influence on the magnetic properties of the superparamagnetic iron oxide NPs. Special attention is given to the selection of molecular anchors for the dispersant shell, because of their importance to ensure colloidal and functional stability of sterically stabilized superparamagnetic iron oxide NPs. We further detail how dispersants have been optimized to gain close control over iron oxide NP stability, size and functionalities by independently considering the influences of anchors and the attached sterically repulsive polymer brushes. A critical evaluation of different strategies to stabilize and functionalize core-shell superparamagnetic iron oxide NPs as well as a brief introduction to characterization methods to compare those strategies is given. This article was submitted as part of a collection of articles on surface nanotechnology for biological applications. Other papers on this topic can be found in issue 2 of vol. 3 (2011). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

Oxidation of nickel-aluminum and iron-aluminum alloys

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

Cathcart, J.V.

1985-01-01

The high-temperature oxidation behavior of several ordered alloys in the Ni-Al and Fe-Al systems is reviewed with special emphasis on Ni/sub 3/Al and NiAl. Ordering influences oxidation through its effect on the activities of the alloy components and by changing the point defect concentration in an alloy. Three categories of Ni-Al alloys are distinguished based on Al content and oxidation behavior. A characteristic feature of the oxidation of high-aluminum Ni-Al and Fe-Al alloys is the formation of voids in the substrate at the oxidate-metal interface. The mechanism of void formation and its suppression by minor additions of oxygen-active elements ismore » discussed. A brief description of the effect of preoxidation on the reactions of Ni/sub 3/Al-base alloys in SO/sub 2//O/sub 2/ environments is also included. 51 references, 14 figures, 1 table.« less

Rapid adsorption of 2,4-dichlorophenoxyacetic acid by iron oxide nanoparticles-doped carboxylic ordered mesoporous carbon.

PubMed

Tang, Lin; Zhang, Sheng; Zeng, Guang-Ming; Zhang, Yi; Yang, Gui-De; Chen, Jun; Wang, Jing-Jing; Wang, Jia-Jia; Zhou, Yao-Yu; Deng, Yao-Cheng

2015-05-01

The ordered mesoporous carbon composite functionalized with carboxylate groups and iron oxide nanoparticles (Fe/OMC) was successfully prepared and used to adsorb 2,4-dichlorophenoxyacetic acid (2,4-D) from wastewater. The resultant adsorbent possessed high degree of order, large specific surface area and pore volume, and good magnetic properties. The increase in initial pollutant concentration and contact time would make the adsorption capacity increase, but the pH and temperature are inversely proportional to 2,4-D uptake. The equilibrium of adsorption was reached within 120 min, and the equilibrated adsorption capacity increased from 99.38 to 310.78 mg/g with the increase of initial concentration of 2,4-D from 100 to 500 mg/L. Notablely, the adsorption capacity reached 97% of the maximum within the first 5 min. The kinetics and isotherm study showed that the pseudo-second-order kinetic and Langmuir isotherm models could well fit the adsorption data. These results indicate that Fe/OMC has a good potential for the rapid adsorption of 2,4-D and prevention of its further diffusion. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

Hydrothermal oxidation in the Biwabik Iron Formation, MN, USA

NASA Astrophysics Data System (ADS)

Losh, Steven; Rague, Ryan

2018-02-01

Precambrian iron formations throughout the world, notably in Australia, Brazil, and South Africa, show evidence of hypogene (≥ 110 °C, mostly > 250 °C) oxidation, alteration, and silica dissolution as a result of tectonic or magmatic activity. Although hydrothermal oxidation has been proposed for the prototype Lake Superior-type iron formation, the Biwabik Iron Formation in Minnesota (USA), it has not been documented there. By examining oxidized and unoxidized Biwabik Iron Formation in three mines, including material from high-angle faults that are associated with oxidation, we document an early hypogene oxidation event ( 175 °C) involving medium-salinity aqueous fluids (8.4 ± 4.9 wt% NaCl equiv) that infiltrated iron formation along high-angle faults. At the Hibbing Taconite Mine, hydrothermal fluids oxidized iron carbonates and silicates near faults, producing goethite ± quartz. In contrast with much of the oxidized iron ores on the Mesabi Range, silica was not removed but rather recrystallized during this event, perhaps lying in a rock-dominated system at low cumulative fluid flux. During the hydrothermal oxidation event in the Hibbing Taconite deposit, quartz-filled microfractures and irregular inclusions commonly formed in coarse variably oxidized magnetite, currently the ore mineral: these inclusions degrade the ore by introducing excess silica in magnetic concentrate. Hydrothermal oxidation at Hibbing Taconite Mine is overprinted by later, relatively minor supergene oxidation both along faults and near the surface, which locally dissolved quartz. At the Fayal Reserve Mine, widespread silicate and carbonate gangue dissolution and iron oxidation was followed by precipitation of pyrite, Mn-siderite, apatite, and other minerals in void spaces, which prevented post-oxidation compaction and significant volume loss in the sampled rocks. Although definitive temperature data for this assemblage are needed, the weight of evidence indicates that this mineralization is hypogene. The association of oxidation with epithermal conditions constrains the oxidation and subsequent mineralization to have taken place during the Precambrian, the only time when these rocks would have experienced the necessary temperatures. The mineralization at Fayal Reserve shows little supergene overprint: pyrite is largely unoxidized. Hydrothermal oxidation in both mines was likely produced by basinal fluids that were expelled during the 1.83-1.87 Ga Penokean Orogeny, and mixing with meteoric fluids along faults, although a 1.1 Ga rift-related fluid flow event is also possible. Later supergene overprinting of the iron formation was minor.

The Iron-Dependent Regulation of the Candida albicans Oxidative Stress Response by the CCAAT-Binding Factor

PubMed Central

Chakravarti, Ananya; Camp, Kyle; McNabb, David S.

2017-01-01

Candida albicans is the most frequently encountered fungal pathogen in humans, capable of causing mucocutaneous and systemic infections in immunocompromised individuals. C. albicans virulence is influenced by multiple factors. Importantly, iron acquisition and avoidance of the immune oxidative burst are two critical barriers for survival in the host. Prior studies using whole genome microarray expression data indicated that the CCAAT-binding factor is involved in the regulation of iron uptake/utilization and the oxidative stress response. This study examines directly the role of the CCAAT-binding factor in regulating the expression of oxidative stress genes in response to iron availability. The CCAAT-binding factor is a heterooligomeric transcription factor previously shown to regulate genes involved in respiration and iron uptake/utilization in C. albicans. Since these pathways directly influence the level of free radicals, it seemed plausible the CCAAT-binding factor regulates genes necessary for the oxidative stress response. In this study, we show the CCAAT-binding factor is involved in regulating some oxidative stress genes in response to iron availability, including CAT1, SOD4, GRX5, and TRX1. We also show that CAT1 expression and catalase activity correlate with the survival of C. albicans to oxidative stress, providing a connection between iron obtainability and the oxidative stress response. We further explore the role of the various CCAAT-binding factor subunits in the formation of distinct protein complexes that modulate the transcription of CAT1 in response to iron. We find that Hap31 and Hap32 can compensate for each other in the formation of an active transcriptional complex; however, they play distinct roles in the oxidative stress response during iron limitation. Moreover, Hap43 was found to be solely responsible for the repression observed under iron deprivation. PMID:28122000

Iron Mossbauer spectral study of weathered Antarctic and SNC meteorites

NASA Technical Reports Server (NTRS)

Solberg, T. C.; Burns, R. G.

1989-01-01

Mossbauer spectral measurements were made on suites of finds from Antarctica and falls collected elsewhere in order to distinguish preterrestrial oxidation products formed on parent meteorite bodies from secondary minerals derived from chemical weathering on earth. Ferric iron is shown to be present throughout the interiors of all the specimens, in amounts ranging from less than 1 to greater than 30 percent Fe(3+). The results indicate that achondrites found to date did not originate from the outermost surface of Mars.

Electronic coupling in iron oxide-modified TiO2 leads to a reduced band gap and charge separation for visible light active photocatalysis.

PubMed

Nolan, Michael

2011-10-28

In recent experiments Tada et al. have shown that TiO(2) surfaces modified with iron oxide display visible light photocatalytic activity. This paper presents first principles simulations of iron oxide clusters adsorbed at the rutile TiO(2) (110) surface to elucidate the origin of the visible light photocatalytic activity of iron oxide modified TiO(2). Small iron oxide clusters adsorb at rutile (110) surface and their presence shifts the valence band so that the band gap of the composite is narrowed towards the visible, thus confirming the origin of the visible light activity of this composite material. The presence of iron oxide at the TiO(2) surface leads to charge separation, which is the origin of enhanced photocatalytic efficiency, consistent with experimental photoluminesence and photocurrent data. Surface modification of a metal oxide is thus an interesting route in the development of visible light photocatalytic materials. This journal is © the Owner Societies 2011

Comparison of Iron and Tungsten Based Oxygen Carriers for Hydrogen Production Using Chemical Looping Reforming

NASA Astrophysics Data System (ADS)

Khan, M. N.; Shamim, T.

2017-08-01

Hydrogen production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative and attractive process. Fossil fuels such as methane are the feedstocks used. This process is similar to a conventional steam-methane reforming but occurs in three steps utilizing an oxygen carrier. As the oxygen carrier plays an important role, its selection should be done carefully. In this study, two oxygen carrier materials of base metal iron (Fe) and tungsten (W) are analysed using a thermodynamic model of a three reactor chemical looping reforming plant in Aspen plus. The results indicate that iron oxide has moderate oxygen carrying capacity and is cheaper since it is abundantly available. In terms of hydrogen production efficiency, tungsten oxide gives 4% better efficiency than iron oxide. While in terms of electrical power efficiency, iron oxide gives 4.6% better results than tungsten oxide. Overall, a TRCLR system with iron oxide is 2.6% more efficient and is cost effective than the TRCLR system with tungsten oxide.

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

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.

Effects of coating spherical iron oxide nanoparticles

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

Milosevic, Irena; Motte, Laurence; Aoun, Bachir

2017-01-01

We investigate the effect of several coatings applied in biomedical applications to iron oxide nanoparticles on the size, structure and composition of the particles. The four structural techniques employed - TEM, DLS, VSM, SAXS and EXAFS - show no significant effects of the coatings on the spherical shape of the bare nanoparticles, the average sizes or the local order around the Fe atoms. The NPs coated with hydroxylmethylene bisphosphonate or catechol have a lower proportion of magnetite than the bare and citrated ones, raising the question whether the former are responsible for increasing the valence state of the oxide onmore » the NP surfaces and lowering the overall proportion of magnetite in the particles. VSM measurements show that these two coatings lead to a slightly higher saturation magnetization than the citrate. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazu and Dr. Federica Migliardo.« less

Synthesis of a sugar-organometallic compound 1,1‧-difurfurylferrocene and its microwave preparation of carbon/iron oxide nanocomposite

NASA Astrophysics Data System (ADS)

Zhao, Shanyu; Cooper, Daniel C.; Xu, Haixun; Zhu, Pinghua; Suggs, J. William

2013-01-01

In order to synthesize a carbon-metal or metal oxide combination sphere, carbonaceous resource furfural 1 was introduced, which was nucleophilic treated with 1,1‧-dilithioferrocene 2 to form a sugar-organometallic compound: ferrocenyl monosaccharide derivative 1,1‧-difurfurylferrocene 3. 1,1‧-Difurfurylferrocene 3 can be hydrothermally treated in a microwave reactor to give 300-500 nm microspheres with the α-Fe2O3 or Fe3O4 nanocrystals formed on the surface, which may be favorable for new magnetic materials preparation or instead of iron with other metal ions, versatile carbon/metal composites will be possibly synthesized for catalysis, drug delivery and magnetic uses.

Development of Sediment Quality Values for Puget Sound. Volume 1.

DTIC Science & Technology

1986-09-01

62 cadmium CHROMIUM,63 chromium COPPER ,64 copper IRON ,65 iron LEAD ,66 lead MANGANES ,67 manganese NICKEL ,68 nickel SELENIUM,69 selenium SILVER ,70...BERYLLIU beryllium 67. CADMIUM cadmium 68. CHROMIUM chromium 69. COPPER copper 70. IRON iron 71. LEAD lead 72. MANGANES manganese 73. NICKEL nickel 74...they can also be strongly influenced by iron and manganese oxide and hydrous oxide surfaces (these phases can scavenge metals under oxidizing

Role of metal oxides in chemical evolution

NASA Astrophysics Data System (ADS)

Kamaluddin

2013-06-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

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

Wang, Zheming; Shi, Zhi; Shi, Liang

2015-08-25

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM)more » were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction. The implications of the observed kinetic behaviors to flavin-mediated Fe(III) oxide reduction in natural environments are discussed.« less

Ferric Oxide Mediated Formation of PCDD/Fs from 2-Monochlorophenol

PubMed Central

Nganai, Shadrack; Lomnicki, Slawo; Dellinger, Barry

2012-01-01

The copper oxide, surface-mediated formation of polychlorinated dibenzop-dioxins and dibenzofurans (PCDD/F) from precursors such as chlorinated phenols is considered to be a major source of PCDD/F emissions from combustion sources. In spite of being present at 2–50x higher concentrations than copper oxide, virtually no studies of the iron oxide-mediated formation of PCDD/F have been reported in the literature. We have performed packed bed, flow reactor studies of the reaction of 50 ppm gas phase 2-monochlorophenol (2-MCP) over a surface of 5% iron oxide on silica over a temperature range of 200–500 °C. Dibenzo-p-dioxin (DD), 1-monochlorodibenzo-p-dioxin (1-MCDD), 4,6-dichlorodibenzofuran (4,6-DCDF), and dibenzofuran (DF) were formed in maximum yields of 0.1, 0.2, 0.3, and 0.4 %, respectively. The yield of PCDD/F over iron oxide peaked at temperatures 50–100 °C higher in temperature than over copper oxide. The maximum yields of DD, 1-MCDD and 4,6-DCDF were 2x and 5x higher over iron oxide, respectively, than over copper oxide, while DF was not observed at all for copper oxide. The resulting PCDD/PCDF ratio was 0.39 versus 1.2 observed for iron oxide and copper oxide, respectively, which is in agreement with PCDD to PCDF ratios in full-scale combustors that are typically ≪1. The combination of 2–50x higher concentrations of iron oxide than copper oxide in most full-scale combustors and 2.5x higher yields of PCDD/F observed in the laboratory, suggest that iron oxide may contribute as much as 5–125x more than copper oxide to the emissions of PCDD/F from full-scale combustors. PMID:19238966

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

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

PubMed

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments

PubMed Central

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-01-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration—a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder. PMID:25871933

Chronic Iron Limitation Confers Transient Resistance to Oxidative Stress in Marine Diatoms.

PubMed

Graff van Creveld, Shiri; Rosenwasser, Shilo; Levin, Yishai; Vardi, Assaf

2016-10-01

Diatoms are single-celled, photosynthetic, bloom-forming algae that are responsible for at least 20% of global primary production. Nevertheless, more than 30% of the oceans are considered "ocean deserts" due to iron limitation. We used the diatom Phaeodactylum tricornutum as a model system to explore diatom's response to iron limitation and its interplay with susceptibility to oxidative stress. By analyzing physiological parameters and proteome profiling, we defined two distinct phases: short-term (<3 d, phase I) and chronic (>5 d, phase II) iron limitation. While at phase I no significant changes in physiological parameters were observed, molecular markers for iron starvation, such as Iron Starvation Induced Protein and flavodoxin, were highly up-regulated. At phase II, down-regulation of numerous iron-containing proteins was detected in parallel to reduction in growth rate, chlorophyll content, photosynthetic activity, respiration rate, and antioxidant capacity. Intriguingly, while application of oxidative stress to phase I and II iron-limited cells similarly oxidized the reduced glutathione (GSH) pool, phase II iron limitation exhibited transient resistance to oxidative stress, despite the down regulation of many antioxidant proteins. By comparing proteomic profiles of P. tricornutum under iron limitation and metatranscriptomic data of an iron enrichment experiment conducted in the Pacific Ocean, we propose that iron-limited cells in the natural environment resemble the phase II metabolic state. These results provide insights into the trade-off between optimal growth rate and susceptibility to oxidative stress in the response of diatoms to iron quota in the marine environment. © 2016 American Society of Plant Biologists. All Rights Reserved.

Chronic Iron Limitation Confers Transient Resistance to Oxidative Stress in Marine Diatoms1

PubMed Central

Graff van Creveld, Shiri; Rosenwasser, Shilo; Vardi, Assaf

2016-01-01

Diatoms are single-celled, photosynthetic, bloom-forming algae that are responsible for at least 20% of global primary production. Nevertheless, more than 30% of the oceans are considered “ocean deserts” due to iron limitation. We used the diatom Phaeodactylum tricornutum as a model system to explore diatom’s response to iron limitation and its interplay with susceptibility to oxidative stress. By analyzing physiological parameters and proteome profiling, we defined two distinct phases: short-term (<3 d, phase I) and chronic (>5 d, phase II) iron limitation. While at phase I no significant changes in physiological parameters were observed, molecular markers for iron starvation, such as Iron Starvation Induced Protein and flavodoxin, were highly up-regulated. At phase II, down-regulation of numerous iron-containing proteins was detected in parallel to reduction in growth rate, chlorophyll content, photosynthetic activity, respiration rate, and antioxidant capacity. Intriguingly, while application of oxidative stress to phase I and II iron-limited cells similarly oxidized the reduced glutathione (GSH) pool, phase II iron limitation exhibited transient resistance to oxidative stress, despite the down regulation of many antioxidant proteins. By comparing proteomic profiles of P. tricornutum under iron limitation and metatranscriptomic data of an iron enrichment experiment conducted in the Pacific Ocean, we propose that iron-limited cells in the natural environment resemble the phase II metabolic state. These results provide insights into the trade-off between optimal growth rate and susceptibility to oxidative stress in the response of diatoms to iron quota in the marine environment. PMID:27503604

Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

NASA Astrophysics Data System (ADS)

Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

2016-11-01

Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

Tucum-Do-Cerrado (Bactris setosa Mart.) Consumption Modulates Iron Homeostasis and Prevents Iron-Induced Oxidative Stress in the Rat Liver

PubMed Central

Fustinoni-Reis, Adriana M.; Arruda, Sandra F.; Dourado, Lívia P. S.; da Cunha, Marcela S. B.; Siqueira, Egle M. A.

2016-01-01

This study investigated the effect of tucum-do-cerrado consumption in the oxidative status of iron-supplemented rats. Four groups of rats were treated: Control (AIN-93G), Tuc (AIN-93G added of tucum-do-cerrado), Fe (AIN-93G iron-enriched), or TucFe (AIN-93G with tucum-do-cerrado and iron-enriched) diet, for 30 days. Iron-enriched diet increased serum, liver, spleen, and intestine iron levels; transferrin saturation; liver lipid oxidation; mRNA levels of hepatic Hamp and Bmp6, and Nrf2 in the intestine. Tucum-do-cerrado consumption reduced spleen lipid and protein oxidation; mRNA levels of hepatic Hamp and Ftl, and increased serum antioxidant capacity and hepatic mRNA levels of Bmp6, Hmox1, Nqo1, and Nrf2. TucFe diet consumption abrogated the liver Hamp iron-induced up-regulation, prevented intestinal iron accumulation; hepatic lipid peroxidation; splenic protein damage, and the increase of catalase, glutathione reductase, and glutathione peroxidase activity in some tissues. These results suggest that tucum-do-cerrado protects tissues against oxidative damage, by reducing iron availability in liver and consequently inhibiting liver Hamp expression. PMID:26901220

Application of Iron Oxide as a pH-dependent Indicator for Improving the Nutritional Quality

PubMed Central

2016-01-01

Acid food indicators can be used as pH indicators for evaluating the quality and freshness of fermented products during the full course of distribution. Iron oxide particles are hardly suspended in water, but partially or completely agglomerated. The agglomeration degree of the iron oxide particles depends on the pH. The pH-dependent particle agglomeration or dispersion can be useful for monitoring the acidity of food. The zeta potential of iron oxide showed a decreasing trend as the pH increased from 2 to 8, while the point of zero charge (PZC) was observed around at pH 6.0-7.0. These results suggested that the size of the iron oxide particles was affected by the change in pH levels. As a result, the particle sizes of iron oxide were smaller at lower pH than at neutral pH. In addition, agglomeration of the iron oxide particles increased as the pH increased from 2 to 7. In the time-dependent aggregation test, the average particle size was 730.4 nm and 1,340.3 nm at pH 2 and 7, respectively. These properties of iron oxide particles can be used to develop an ideal acid indicator for food pH and to monitor food quality, besides a colorant or nutrient for nutrition enhancement and sensory promotion in food industry. PMID:27482521

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

Responses of Saccharomyces cerevisiae Strains from Different Origins to Elevated Iron Concentrations

PubMed Central

Martínez-Garay, Carlos Andrés; de Llanos, Rosa; Romero, Antonia María; Martínez-Pastor, María Teresa

2016-01-01

Iron is an essential micronutrient for all eukaryotic organisms. However, the low solubility of ferric iron has tremendously increased the prevalence of iron deficiency anemia, especially in women and children, with dramatic consequences. Baker's yeast Saccharomyces cerevisiae is used as a model eukaryotic organism, a fermentative microorganism, and a feed supplement. In this report, we explore the genetic diversity of 123 wild and domestic strains of S. cerevisiae isolated from different geographical origins and sources to characterize how yeast cells respond to elevated iron concentrations in the environment. By using two different forms of iron, we selected and characterized both iron-sensitive and iron-resistant yeast strains. We observed that when the iron concentration in the medium increases, iron-sensitive strains accumulate iron more rapidly than iron-resistant isolates. We observed that, consistent with excess iron leading to oxidative stress, the redox state of iron-sensitive strains was more oxidized than that of iron-resistant strains. Growth assays in the presence of different oxidative reagents ruled out that this phenotype was due to alterations in the general oxidative stress protection machinery. It was noteworthy that iron-resistant strains were more sensitive to iron deficiency conditions than iron-sensitive strains, which suggests that adaptation to either high or low iron is detrimental for the opposite condition. An initial gene expression analysis suggested that alterations in iron homeostasis genes could contribute to the different responses of distant iron-sensitive and iron-resistant yeast strains to elevated environmental iron levels. PMID:26773083

Role of clay minerals in the transportation of iron

USGS Publications Warehouse

Carroll, D.

1958-01-01

The clay minerals have iron associated with them in several ways: 1. (1) as an essential constituent 2. (2) as a minor constituent within the crystal lattice where it is in isomorphous substitution and 3. (3) as iron oxide on the surface of the mineral platelets. Nontronite, "hydromica," some chlorites, vermiculite, glauconite and chamosite contain iron as an essential constituent. Kaolinite and halloysite have no site within the lattice for iron, but in certain environments iron oxide (goethite or hematite) is intimately associated as a coating on the micelles. Analyses of clay minerals show that the content of Fe2O3 varies: 29 per cent (nontronite), 7??3 per cent (griffithite), 4.5 per cent ("hydromica"), 5.5 per cent (chlorite), 4 per cent (vermiculite) and 18 per cent (glauconite). The FeO content is: 40 per cent (chamosite), 7.8 per cent (griffithite), 1-2 per cent ("hydromica"), 3 per cent (glauconite) and 2 per cent (chlorite). The iron associated with the clay minerals remains stable in the environment in which the minerals occur, but if either pH or Eh or both are changed the iron may be affected. Change of environment will cause: 1. (1) removal of iron by reduction of Fe3+ to Fe2+; 2. (2) ion-exchange reactions; 3. (3) instability of the crystal lattice. Experiments using bacterial activity to produce reducing conditions with kaolinite and halloysite coated with iron oxides and with nontronite in which ferric iron is in the octahedral position within the lattice showed that ferric oxide is removed at Eh +0??215 in fresh water and at Eh +0.098 in sea water. Hematite, goethite, and indefinite iron oxides were removed at different rates. Red ferric oxides were changed to black indefinite noncrystalline ferrous sulphide at Eh -0.020 but reverted to ferric oxide under oxidizing conditions. Nontronite turned bright green under reducing conditions and some of the ferrous iron remained within the lattice on a return to oxidizing conditions. Bacterial activity seems to be necessary for maintaining reducing conditions in the environments studied. ?? 1958.

Influence of iron solubility and charged surface-active compounds on lipid oxidation in fatty acid ethyl esters containing association colloids.

PubMed

Homma, Rika; Johnson, David R; McClements, D Julian; Decker, Eric A

2016-05-15

The impact of iron compounds with different solubilities on lipid oxidation was studied in the presence and absence of association colloids. Iron (III) sulfate only accelerated lipid oxidation in the presence of association colloids while iron (III) oleate accelerated oxidation in the presence and absence of association colloids. Further, iron (III) oxide retarded lipid oxidation both with and without association colloids. The impact of charged association colloids on lipid oxidation in ethyl oleate was also investigated. Association colloids consisting of the anionic surface-active compound dodecyl sulphosuccinate sodium salt (AOT), cationic surface-active compound hexadecyltrimethylammonium bromide (CTAB), and nonionic surface-active compound 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100) retarded, promoted, and had no effect on lipid oxidation rates, respectively. These results indicate that the polarity of metal compounds and the charge of association colloids play a big role in lipid oxidation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of atmospheric processes on the solubility and composition of iron in Saharan dust

DOE PAGES

Longo, Amelia F.; Feng, Yan; Lai, Barry; ...

2016-06-10

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation statemore » became more reduced, and aerosol acidity increased. As a result, atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.« less

Influence of Atmospheric Processes on the Solubility and Composition of Iron in Saharan Dust.

PubMed

Longo, Amelia F; Feng, Yan; Lai, Barry; Landing, William M; Shelley, Rachel U; Nenes, Athanasios; Mihalopoulos, Nikolaos; Violaki, Kalliopi; Ingall, Ellery D

2016-07-05

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation state became more reduced, and aerosol acidity increased. Atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.

Roles of lipocalin 2 and adiponectin in iron overload cardiomyopathy.

PubMed

Siri-Angkul, Natthaphat; Chattipakorn, Siriporn C; Chattipakorn, Nipon

2018-07-01

Thalassemia is among the most common genetic diseases worldwide. Ineffective erythropoiesis, chronic hemolysis, and regular blood transfusion in thalassemia patients lead to increased iron burden. Iron overload cardiomyopathy is the most severe co-morbidity and most common cause of mortality in thalassemia patients. Although its associated mechanisms are still not completely understood, cellular iron mishandling, chronic inflammation, and oxidative stress appear to be the key processes involved. In order to acquire a more comprehensive insight of the impact of cardiac iron overload, these alterations need to be intensively investigated. This comprehensive mini-review focuses on two emergent molecules which have been shown to potentially play significant roles in iron overload cardiomyopathy. These two molecules are an iron-transporting protein, lipocalin 2, and an anti-inflammatory adipokine, adiponectin. Reports from in vitro and in vivo studies are comprehensively summarized. Clinical studies examining the roles of these molecules in thalassemia patients are also presented and discussed. © 2017 Wiley Periodicals, Inc.

Intensification of the Reverse Cationic Flotation of Hematite Ores with Optimization of Process and Hydrodynamic Parameters of Flotation Cell

NASA Astrophysics Data System (ADS)

Poperechnikova, O. Yu; Filippov, L. O.; Shumskaya, E. N.; Filippova, I. V.

2017-07-01

The demand of high grade iron ore concentrates is a major issue due to the depletion of rich iron-bearing ores and high competitiveness in the iron ore market. Iron ore production is forced out to upgrade flowsheets to decrease the silica content in the pelettes. Different types of ore have different mineral composition and texture-structural features which require different mineral processing methods and technologies. The paper presents a comparative study of the cationic and anionic flotation routes to process a fine-grain oxidized iron ore. The modified carboxymethyl cellulose was found as the most efficient depressant in reverse cationic flotation. The results of flotation optimization of hematite ores using matrix of second-order center rotatable uniform design allowed to define the collector concentration, impeller rotation speed and air flowrate as the main flotation parameters impacting on the iron ore concentrate quality and iron recovery in a laboratory flotation machine. These parameters have been selected as independent during the experiments.

Reactive Iron and Iron-Reducing Bacteria in Louisiana Continental Shelf Sediments

EPA Science Inventory

The Mississippi and Atchafalaya Rivers release sediments containing 15 x 106 t of iron onto the Louisiana continental shelf (LCS) each year. Iron oxides reaching the seafloor may be utilized as electron acceptors by iron-reducing bacteria for organic matter oxidation or become r...

Atmospheric hydrogen peroxide and Eoarchean iron formations.

PubMed

Pecoits, E; Smith, M L; Catling, D C; Philippot, P; Kappler, A; Konhauser, K O

2015-01-01

It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earth's oldest IF. © 2014 John Wiley & Sons Ltd.

Methyltrimethoxysilane (MTMS)-based silica-iron oxide superhydrophobic nanocomposites.

PubMed

Nadargi, Digambar; Gurav, Jyoti; Marioni, Miguel A; Romer, Sara; Matam, Santhosh; Koebel, Matthias M

2015-12-01

We report a facile synthesis of superhydrophobic silica-iron oxide nanocomposites via a co-precursor sol-gel process. The choice of the silica precursor (Methyltrimethoxysilane, MTMS) in combination with iron nitrate altered the pore structure dramatically. The influence of iron oxide doping on the structural properties of pristine MTMS aerogel is discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

USGS Publications Warehouse

Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

2009-01-01

Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

Importance of a martian hematite site for astrobiology

NASA Technical Reports Server (NTRS)

Allen, C. C.; Westall, F.; Schelble, R. T.

2001-01-01

Defining locations where conditions may have been favorable for life is a key objective for the exploration of Mars. Of prime importance are sites where conditions may have been favorable for the preservation of evidence of prebiotic or biotic processes. Areas displaying significant concentrations of the mineral hematite (alpha-Fe2O3), recently identified by thermal emission spectrometry, may have significance in the search for evidence of extraterrestrial life. Since iron oxides can form as aqueous mineral precipitates, the potential exists to preserve microscopic evidence of life in iron oxide-depositing ecosystems. Terrestrial hematite deposits proposed as possible analogs for hematite deposits on Mars include massive (banded) iron formations, iron oxide hydrothermal deposits, iron-rich laterites and ferricrete soils, and rock varnish. We report the potential for long-term preservation of microfossils by iron oxide mineralization in specimens of the approximately 2,100-Ma banded iron deposit of the Gunflint Formation, Canada. Scanning and analytical electron microscopy reveals micrometer-scale rods, spheres, and filaments consisting predominantly of iron and oxygen with minor carbon. We interpret these objects as microbial cells permineralized by an iron oxide, presumably hematite. The confirmation of ancient martian microbial life in hematite deposits will require the return of samples to terrestrial laboratories. A hematite-rich deposit composed of aqueous iron oxide precipitates may thus prove to be a prime site for future sample return.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces.Iron oxide/SnO2 magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO2 quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO2 core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe2O3 seeds and commercial SnO2 products, mainly owing to the effective electron hole separation at the iron oxides/SnO2 interfaces. Electronic supplementary information (ESI) available: TEM and HRTEM images of hematite seeds and iron oxide/SnO2 (12 h and 36 h). See DOI: 10.1039/c1nr10728c

Multifunctional gold coated iron oxide core-shell nanoparticles stabilized using thiolated sodium alginate for biomedical applications.

PubMed

Sood, Ankur; Arora, Varun; Shah, Jyoti; Kotnala, R K; Jain, Tapan K

2017-11-01

In this paper we report synthesis of aqueous based gold coated iron oxide nanoparticles to integrate the localized surface plasma resonance (SPR) properties of gold and magnetic properties of iron oxide in a single system. Iron oxide-gold core shell nanoparticles were stabilized by attachment of thiolated sodium alginate to the surface of nanoparticles. Transmission electron microscope (TEM) micrograph presents an average elementary particle size of 8.1±2.1nm. High resolution TEM (HR-TEM) and X-ray photon spectroscopy further confirms the presence of gold shell around iron oxide core. Gold coating is responsible for reducing saturation magnetization (M s ) value from ~41emu/g to ~24emu/g - in thiolated sodium alginate stabilized gold coated iron oxide core-shell nanoparticles. The drug (curcumin) loading efficiency for the prepared nanocomposites was estimated to be around 7.2wt% (72μgdrug/mg nanoparticles) with encapsulation efficiency of 72.8%. Gold-coated iron oxide core-shell nanoparticles could be of immense importance in the field of targeted drug delivery along with capability to be used as contrast agent for MRI & CT. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

NASA Astrophysics Data System (ADS)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

Fenton-like oxidation of 2,4-DCP in aqueous solution using iron-based nanoparticles as the heterogeneous catalyst.

PubMed

Li, Renchao; Gao, Ying; Jin, Xiaoying; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravendra

2015-01-15

In this report, various iron-based nanoparticles (nZVI, n-Ni/Fe, n-Pd/Fe) were used for both heterogeneous Fenton oxidation of 2,4-dichlorophenol (2,4-DCP) and reductive dechlorination of 2,4-DCP in order to understand their roles in the Fenton oxidation and the reductive degradation of 2,4-DCP. The dechlorination efficiency of 2,4-DCP using nZVI, n-Ni/Fe, n-Fe/Pd and Fe(2)(+) was 6.48%, 6.80%, 15.95%, 5.02%, while Fenton oxidation efficiency of 2,4-DCP was 57.87%, 34.23%, 27.94%, 19.61% after 180 min, respectively. The new findings included a higher dechlorination using n-Fe/Pd due to Pd effective catalysis and the effective heterogeneous Fenton oxidation using nZVI depending on reductive dechlorination and heterogeneous Fenton oxidation occurs simultaneously. However, nZVI as the potential catalyst for heterogeneous Fenton was observed, and SEM, EDS and XRD demonstrate that change on the nZVI surface occurred due to the Fe(2+) leaching, and Total Organic Carbon (TOC) (30.71%) shows that 2,4-DCP was degraded. Furthermore, the experiment indicates that the pH values and concentration of 2,4-DCP significantly impacted on the heterogeneous Fenton oxidation of 2,4-DCP and the data fits well with the pseudo first-order kinetic model, which was a diffusion-controlled reaction. Finally, a possible mechanism for degradation of 2,4-DCP was proposed. Copyright © 2014 Elsevier Inc. All rights reserved.

Iron Oxide Deposition from Aqueous Solution and Iron Formations on Mars

NASA Technical Reports Server (NTRS)

Catling, David; Moore, Jeff

2000-01-01

Iron formations are ancient, laminated chemical sediments containing at least 15 wt% Fe. We discuss possible mechanisms for their formation in aqueous environments on early Mars. Such iron oxide deposits may be detectable today.

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.

Retinal iron homeostasis in health and disease

PubMed Central

Song, Delu; Dunaief, Joshua L.

2013-01-01

Iron is essential for life, but excess iron can be toxic. As a potent free radical creator, iron generates hydroxyl radicals leading to significant oxidative stress. Since iron is not excreted from the body, it accumulates with age in tissues, including the retina, predisposing to age-related oxidative insult. Both hereditary and acquired retinal diseases are associated with increased iron levels. For example, retinal degenerations have been found in hereditary iron overload disorders, like aceruloplasminemia, Friedreich's ataxia, and pantothenate kinase-associated neurodegeneration. Similarly, mice with targeted mutation of the iron exporter ceruloplasmin and its homolog hephaestin showed age-related retinal iron accumulation and retinal degeneration with features resembling human age-related macular degeneration (AMD). Post mortem AMD eyes have increased levels of iron in retina compared to age-matched healthy donors. Iron accumulation in AMD is likely to result, in part, from inflammation, hypoxia, and oxidative stress, all of which can cause iron dysregulation. Fortunately, it has been demonstrated by in vitro and in vivo studies that iron in the retinal pigment epithelium (RPE) and retina is chelatable. Iron chelation protects photoreceptors and retinal pigment epithelial cells (RPE) in a variety of mouse models. This has therapeutic potential for diminishing iron-induced oxidative damage to prevent or treat AMD. PMID:23825457

Enhanced Fenton-like removal of nitrobenzene via internal microelectrolysis in nano zerovalent iron/activated carbon composite.

PubMed

Hu, Sihai; Wu, Yaoguo; Yao, Hairui; Lu, Cong; Zhang, Chengjun

2016-01-01

The efficiency of Fenton-like catalysis using nano zerovalent iron (nZVI) is limited by nZVI aggregation and activity loss due to inactive ferric oxide forming on the nZVI surface, which hinders electron transfer. A novel iron-carbon composite catalyst consisting of nZVI and granular activated carbon (GAC), which can undergo internal iron-carbon microelectrolysis spontaneously, was successfully fabricated by the adsorption-reduction method. The catalyst efficiency was evaluated in nitrobenzene (NB) removal via the Fenton-like process (H2O2-nZVI/GAC). The results showed that nZVI/GAC composite was good for dispersing nZVI on the surface of GAC, which permitted much better removal efficiency (93.0%) than nZVI (31.0%) or GAC (20.0%) alone. Moreover, iron leaching decreased from 1.28 to 0.58 mg/L after reaction of 240 min and the oxidation kinetic of the Fenton-like reaction can be described well by the second-order reaction kinetic model (R2=0.988). The composite catalyst showed sustainable catalytic ability and GAC performed as a medium for electron transfer in internal iron-carbon microelectrolysis to promote Fe2+ regeneration and Fe3+/Fe2+ cycles. Therefore, this study represents an important method to design a low cost and high efficiency Fenton-like catalyst in practical application.

Electropulse treatment of water solution of humic substances in a layer iron granules in process of water treatment

NASA Astrophysics Data System (ADS)

Lobanova, G. L.; Yurmazova, T. A.; Shiyan, L. N.; Machekhina, K. I.

2016-02-01

The present work is a part of a continuations study of the physical and chemical processes complex in natural waters containing humic-type organic substances at the influence of pulsed electrical discharges in a layer of iron pellets. The study of humic substances processing in the iron granules layer by means of pulsed electric discharge for the purpose of water purification from organic compounds humic origin from natural water of the northern regions of Russia is relevant for the water treatment technologies. In case of molar humate sodium - iron ions (II) at the ratio 2:3, reduction of solution colour and chemical oxygen demand occur due to the humate sodium ions and iron (II) participation in oxidation-reduction reactions followed by coagulation insoluble compounds formation at a pH of 6.5. In order to achieve this molar ratio and the time of pulsed electric discharge, equal to 10 seconds is experimentally identified. The role of secondary processes that occur after disconnection of the discharge is shown. The time of contact in active erosion products with sodium humate, equal to 1 hour is established. During this time, the value of permanganate oxidation and iron concentration in solution achieves the value of maximum permissible concentrations and further contact time increase does not lead to the controlled parameters change.

Electrolytic Manipulation of Persulfate Reactivity by Iron Electrodes for TCE Degradation in Groundwater

PubMed Central

Yuan, Songhu; Liao, Peng; Alshawabkeh, Akram N.

2014-01-01

Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater, and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053•Iv + 0.059 (−122 A/m3 ≤ Iv ≤ 244 A/m3) where k1 and Iv are the pseudo first-order rate constant (min−1) and volume normalized current (A/m3), respectively. Persulfate is mainly decomposed by Fe2+ produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe3+ reduction on the cathode. SO4•− and •OH co-contribute to TCE degradation, but •OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface. PMID:24328192

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

Longo, Amelia F.; Feng, Yan; Lai, Barry

Aerosol iron was examined in Saharan dust plumes using a combination of iron near-edge X-ray absorption spectroscopy and wet-chemical techniques. Aerosol samples were collected at three sites located in the Mediterranean, the Atlantic, and Bermuda to characterize iron at different atmospheric transport lengths and time scales. Iron(III) oxides were a component of aerosols at all sampling sites and dominated the aerosol iron in Mediterranean samples. In Atlantic samples, iron(II and III) sulfate, iron(III) phosphate, and iron(II) silicates were also contributors to aerosol composition. With increased atmospheric transport time, iron(II) sulfates are found to become more abundant, aerosol iron oxidation statemore » became more reduced, and aerosol acidity increased. As a result, atmospheric processing including acidic reactions and photoreduction likely influence the form of iron minerals and oxidation state in Saharan dust aerosols and contribute to increases in aerosol-iron solubility.« less

A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

PubMed

Ding, Chunyan; Zhou, Weiwei; Wang, Bin; Li, Xin; Wang, Dong; Zhang, Yong; Wen, Guangwu

2017-08-25

Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex

DOE PAGES

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong -Min; ...

2017-09-29

Here, a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe V(NTs)(TAML)] – (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe V(NTs)(TAML +•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML +•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

Genomic insights into microbial iron oxidation and iron uptake strategies in extremely acidic environments.

PubMed

Bonnefoy, Violaine; Holmes, David S

2012-07-01

This minireview presents recent advances in our understanding of iron oxidation and homeostasis in acidophilic Bacteria and Archaea. These processes influence the flux of metals and nutrients in pristine and man-made acidic environments such as acid mine drainage and industrial bioleaching operations. Acidophiles are also being studied to understand life in extreme conditions and their role in the generation of biomarkers used in the search for evidence of existing or past extra-terrestrial life. Iron oxidation in acidophiles is best understood in the model organism Acidithiobacillus ferrooxidans. However, recent functional genomic analysis of acidophiles is leading to a deeper appreciation of the diversity of acidophilic iron-oxidizing pathways. Although it is too early to paint a detailed picture of the role played by lateral gene transfer in the evolution of iron oxidation, emerging evidence tends to support the view that iron oxidation arose independently more than once in evolution. Acidic environments are generally rich in soluble iron and extreme acidophiles (e.g. the Leptospirillum genus) have considerably fewer iron uptake systems compared with neutrophiles. However, some acidophiles have been shown to grow as high as pH 6 and, in the case of the Acidithiobacillus genus, to have multiple iron uptake systems. This could be an adaption allowing them to respond to different iron concentrations via the use of a multiplicity of different siderophores. Both Leptospirillum spp. and Acidithiobacillus spp. are predicted to synthesize the acid stable citrate siderophore for Fe(III) uptake. In addition, both groups have predicted receptors for siderophores produced by other microorganisms, suggesting that competition for iron occurs influencing the ecophysiology of acidic environments. Little is known about the genetic regulation of iron oxidation and iron uptake in acidophiles, especially how the use of iron as an energy source is balanced with its need to take up iron for metabolism. It is anticipated that integrated and complex regulatory networks sensing different environmental signals, such as the energy source and/or the redox state of the cell as well as the oxygen availability, are involved. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Nanomagnetism study of highly-ordered iron oxide nanocrystal assemblies fabricated by the Langmuir-Blodgett technique.

PubMed

Zhang, HaiTao; Bao, NiNa; Yuan, Du; Ding, Jun

2013-09-21

Iron oxide nanocrystals are ideal building blocks for the construction of flexible nanodevices whose performance can be modulated by controlling the morphology of isolated particles and their organizational form. This work demonstrates the fabrication of high quality Langmuir-Blodgett (LB) nanocrystal assemblies with limited overlapping and higher coverage by systemically and combinatorially optimizing the parameters of compression pressure and quantity of spread nanocrystals. Monodispersed iron oxide nanocrystals with a diameter of 11.8 nm were synthesized by thermal decomposition of Fe(CO)5 in trioctylamine with the presence of oleic acid. Multilayer nanocrystal assemblies were obtained through a layer-by-layer (LBL) process by repeating the transfer procedure after their hydrophilicity had been improved via treatment in a UV-ozone oven. The quality of nanocrystal assemblies was investigated by UV-vis spectrometry and scanning electron microscopy. The nanomagnetism for the nanostructures of different combination manners was studied systemically by a superconducting quantum interference device (SQUID). A lower superparamagnetic blocking temperature was found in the monolayer Fe3O4 nanocrystal assembly. The superparamagnetic blocking temperature in magnetic nanocrystal assemblies could be tuned through modifying the interparticle interactions among the interlayer and intralayers by controlling the layer number of the assemblies.

Determination of oxidation state of iron in normal and pathologically altered human aortic valves

NASA Astrophysics Data System (ADS)

Czapla-Masztafiak, J.; Lis, G. J.; Gajda, M.; Jasek, E.; Czubek, U.; Bolechała, F.; Borca, C.; Kwiatek, W. M.

2015-12-01

In order to investigate changes in chemical state of iron in normal and pathologically altered human aortic valves X-ray absorption spectroscopy was applied. Since Fe is suspected to play detrimental role in aortic valve stenosis pathogenesis the oxidation state of this element has been determined. The experimental material consisted of 10 μm sections of valves excised during routine surgery and from autopsies. The experiment was performed at the MicroXAS beamline of the SLS synchrotron facility in Villigen (Switzerland). The Fe K-edge XANES spectra obtained from tissue samples were carefully analyzed and compared with the spectra of reference compounds containing iron in various chemical structures. The analysis of absorption edge position and shape of the spectra revealed that both chemical forms of iron are presented in valve tissue but Fe3+ is the predominant form. Small shift of the absorption edge toward higher energy in the spectra from stenotic valve samples indicates higher content of the Fe3+ form in pathological tissue. Such a phenomenon suggests the role of Fenton reaction and reactive oxygen species in the etiology of aortic valve stenosis. The comparison of pre-edge regions of XANES spectra for control and stenotic valve tissue confirmed no differences in local symmetry or spin state of iron in analyzed samples.

Toxicokinetics and biodistribution of dextran stabilized iron oxide nanoparticles in rats

NASA Astrophysics Data System (ADS)

Easo, S. L.; Neelima, R.; Mohanan, P. V.

2015-07-01

Dextran stabilized iron oxide nanoparticles (DIONPs) synthesized and characterized for hyperthermia application were tested for toxicokinetics and biodistribution in order to analyze the prospect of safety and biocompatibility of these particles for advanced use. Rats were administered a single dose of DIONPs at a concentration of 10 mg kg-1 by intravenous injection with a post-exposure period of 1, 7, 14 and 28 days. Liver, spleen, kidney, blood, urine and feces were examined for iron content by inductively coupled plasma atomic emission spectroscopy. At 24 h, greater amounts of nanoparticles were deposited in liver and spleen. Maximum absorption of iron in blood occurred at day 7 and excess iron appeared to be eliminated by liver, seemingly via biliary excretion. Serum hematology and biochemistry analysis revealed an overall lack of systemic toxicity due to metabolism of DIONPs. Additionally, pathological changes associated with repeated exposure to DIONPs with a post exposure period of 28 days were also assessed. Although no significant pathological alterations were seen in spleen or kidney, slight morphological deviations from normal were observed in liver. Further progression in the analysis of biological response towards DIONPs will be determined in long-term studies in the presence of an alternating magnetic field in the context of hyperthermia application.

Molecular Beam Epitaxial Growth of Iron Nitrides on Zinc-Blende Gallium Nitride(001)

NASA Astrophysics Data System (ADS)

Pak, Jeongihm; Lin, Wenzhi; Chinchore, Abhijit; Wang, Kangkang; Smith, Arthur R.

2008-03-01

Iron nitrides are attractive materials for their high magnetic moments, corrosion, and oxidation resistance. We present the successful epitaxial growth of iron nitride on zinc-blende gallium nitride (c-GaN) in order to develop a novel magnetic transition metal nitride/semiconductor system. First, GaN is grown on magnesium oxide (MgO) substrates having (001) orientation using rf N2-plasma molecular beam epitaxy. Then we grow FeN at substrate temperature of ˜ 210 ^oC up to a thickness of ˜ 10.5 nm. In-situ reflection high-energy electron diffraction (RHEED) is used to monitor the surface during growth. Initial results suggest that the epitaxial relationship is FeN[001] || GaN[001] and FeN[100] || GaN[100]. Work in progress is to investigate the surface using in-situ scanning tunneling microscopy (STM) to reveal the surface structure at atomic scale, as well as to explore more Fe-rich magnetic phases.

Controlled atmosphere for fabrication of cermet electrodes

DOEpatents

Ray, Siba P.; Woods, Robert W.

1998-01-01

A process for making an inert electrode composite wherein a metal oxide and a metal are reacted in a gaseous atmosphere at an elevated temperature of at least about 750.degree. C. The metal oxide is at least one of the nickel, iron, tin, zinc and zirconium oxides and the metal is copper, silver, a mixture of copper and silver or a copper-silver alloy. The gaseous atmosphere has an oxygen content that is controlled at about 5-3000 ppm in order to obtain a desired composition in the resulting composite.

Controlled atmosphere for fabrication of cermet electrodes

DOEpatents

Ray, S.P.; Woods, R.W.

1998-08-11

A process is disclosed for making an inert electrode composite wherein a metal oxide and a metal are reacted in a gaseous atmosphere at an elevated temperature of at least about 750 C. The metal oxide is at least one of the nickel, iron, tin, zinc and zirconium oxides and the metal is copper, silver, a mixture of copper and silver or a copper-silver alloy. The gaseous atmosphere has an oxygen content that is controlled at about 5--3000 ppm in order to obtain a desired composition in the resulting composite. 2 figs.

Structural characterization, antibacterial and catalytic effect of iron oxide nanoparticles synthesised using the leaf extract of Cynometra ramiflora

NASA Astrophysics Data System (ADS)

Groiss, Silvia; Selvaraj, Raja; Varadavenkatesan, Thivaharan; Vinayagam, Ramesh

2017-01-01

In the present investigation, the leaf extract of Cynometra ramiflora was used to synthesize iron oxide nanoparticles. Within minutes of adding iron sulphate to the leaf extract, iron oxide nanoparticles were formed and thus, the method is very simple and fast. UV-VIS spectra showed the strong absorption band in the visible region. SEM images showed discrete spherical shaped particles and EDS spectra confirmed the iron and oxygen presence. The XRD results depicted the crystalline structure of iron oxide nanoparticles. FT-IR spectra portrayed the existence of functional groups of phytochemicals which are probably involved in the formation and stabilization of nanoparticles. The iron oxide nanoparticles exhibited effective inhibition against E. coli and S. epidermidis which may find its applications in the antibacterial drug development. Furthermore, the catalytic activity of the nanoparticles as Fenton-like catalyst was successfully investigated for the degradation of Rhodamine-B dye. This outcome could play a prominent role in the wastewater treatment.

Recent progress in magnetic iron oxide-semiconductor composite nanomaterials as promising photocatalysts

NASA Astrophysics Data System (ADS)

Wu, Wei; Changzhong Jiang, Affc; Roy, Vellaisamy A. L.

2014-11-01

Photocatalytic degradation of toxic organic pollutants is a challenging tasks in ecological and environmental protection. Recent research shows that the magnetic iron oxide-semiconductor composite photocatalytic system can effectively break through the bottleneck of single-component semiconductor oxides with low activity under visible light and the challenging recycling of the photocatalyst from the final products. With high reactivity in visible light, magnetic iron oxide-semiconductors can be exploited as an important magnetic recovery photocatalyst (MRP) with a bright future. On this regard, various composite structures, the charge-transfer mechanism and outstanding properties of magnetic iron oxide-semiconductor composite nanomaterials are sketched. The latest synthesis methods and recent progress in the photocatalytic applications of magnetic iron oxide-semiconductor composite nanomaterials are reviewed. The problems and challenges still need to be resolved and development strategies are discussed.

Curcumin Attenuates Iron Accumulation and Oxidative Stress in the Liver and Spleen of Chronic Iron-Overloaded Rats

PubMed Central

Badria, Farid A.; Ibrahim, Ahmed S.; Badria, Adel F.; Elmarakby, Ahmed A.

2015-01-01

Objectives Iron overload is now recognized as a health problem in industrialized countries, as excessive iron is highly toxic for liver and spleen. The potential use of curcumin as an iron chelator has not been clearly identified experimentally in iron overload condition. Here, we evaluate the efficacy of curcumin to alleviate iron overload-induced hepatic and splenic abnormalities and to gain insight into the underlying mechanisms. Design and Methods Three groups of male adult rats were treated as follows: control rats, rats treated with iron in a drinking water for 2 months followed by either vehicle or curcumin treatment for 2 more months. Thereafter, we studied the effects of curcumin on iron overload-induced lipid peroxidation and anti-oxidant depletion. Results Treatment of iron-overloaded rats with curcumin resulted in marked decreases in iron accumulation within liver and spleen. Iron-overloaded rats had significant increases in malonyldialdehyde (MDA), a marker of lipid peroxidation and nitric oxide (NO) in liver and spleen when compared to control group. The effects of iron overload on lipid peroxidation and NO levels were significantly reduced by the intervention treatment with curcumin (P<0.05). Furthermore, the endogenous anti-oxidant activities/levels in liver and spleen were also significantly decreased in chronic iron overload and administration of curcumin restored the decrease in the hepatic and splenic antioxidant activities/levels. Conclusion Our study suggests that curcumin may represent a new horizon in managing iron overload-induced toxicity as well as in pathological diseases characterized by hepatic iron accumulation such as thalassemia, sickle cell anemia, and myelodysplastic syndromes possibly via iron chelation, reduced oxidative stress derived lipid peroxidation and improving the body endogenous antioxidant defense mechanism. PMID:26230491

Aortic iron overload with oxidative stress and inflammation in human and murine abdominal aortic aneurysm.

PubMed

Sawada, Hisashi; Hao, Hiroyuki; Naito, Yoshiro; Oboshi, Makiko; Hirotani, Shinichi; Mitsuno, Masataka; Miyamoto, Yuji; Hirota, Seiichi; Masuyama, Tohru

2015-06-01

Although iron is an essential element for maintaining physiological function, excess iron leads to tissue damage caused by oxidative stress and inflammation. Oxidative stress and inflammation play critical roles for the development of abdominal aortic aneurysm (AAA). However, it has not been investigated whether iron plays a role in AAA formation through oxidative stress and inflammation. We, therefore, examined whether iron is involved in the pathophysiology of AAA formation using human AAA walls and murine AAA models. Human aortic walls were collected from 53 patients who underwent cardiovascular surgery (non-AAA=34; AAA=19). Murine AAA was induced by infusion of angiotensin II to apolipoprotein E knockout mice. Iron was accumulated in human and murine AAA walls compared with non-AAA walls. Immunohistochemistry showed that both 8-hydroxy-2'-deoxyguanosine and CD68-positive areas were increased in AAA walls compared with non-AAA walls. The extent of iron accumulated area positively correlated with that of 8-hydroxy-2'-deoxyguanosine expression area and macrophage infiltration area in human and murine AAA walls. We next investigated the effects of dietary iron restriction on AAA formation in mice. Iron restriction reduced the incidence of AAA formation with attenuation of oxidative stress and inflammation. Aortic expression of transferrin receptor 1, intracellular iron transport protein, was increased in human and murine AAA walls, and transferrin receptor 1-positive area was similar to areas where iron accumulated and F4/80 were positive. Iron is involved in the pathophysiology of AAA formation with oxidative stress and inflammation. Dietary iron restriction could be a new therapeutic strategy for AAA progression. © 2015 American Heart Association, Inc.

A method for recovery of iron, titanium, and vanadium from vanadium-bearing titanomagnetite

NASA Astrophysics Data System (ADS)

Zhang, Yi-min; Wang, Li-na; Chen, De-sheng; Wang, Wei-jing; Liu, Ya-hui; Zhao, Hong-xin; Qi, Tao

2018-02-01

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Effect of oxidative stress induced by intracranial iron overload on central pain after spinal cord injury.

PubMed

Meng, Fan Xing; Hou, Jing Ming; Sun, Tian Sheng

2017-02-08

Central pain (CP) is a common clinical problem in patients with spinal cord injury (SCI). Recent studies found the pathogenesis of CP was related to the remodeling of the brain. We investigate the roles of iron overload and subsequent oxidative stress in the remodeling of the brain after SCI. We established a rat model of central pain after SCI. Rats were divided randomly into four groups: SCI, sham operation, SCI plus deferoxamine (DFX) intervention, and SCI plus nitric oxide synthase (NOS) inhibitor treatment. Pain behavior was observed and thermal pain threshold was measured regularly, and brain levels of iron, transferrin receptor 1 (TfR1), ferritin (Fn), and lactoferrin (Lf), were detected in the different groups 12 weeks after establishment of the model. Rats demonstrated self-biting behavior after SCI. Furthermore, the latent period of thermal pain was reduced and iron levels in the hind limb sensory area, hippocampus, and thalamus increased after SCI. Iron-regulatory protein (IRP) 1 levels increased in the hind limb sensory area, while Fn levels decreased. TfR1 mRNA levels were also increased and oxidative stress was activated. Oxidative stress could be inhibited by ferric iron chelators and NOS inhibitors. SCI may cause intracranial iron overload through the NOS-iron-responsive element/IRP pathway, resulting in central pain mediated by the oxidative stress response. Iron chelators and oxidative stress inhibitors can effectively relieve SCI-associated central pain.

Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC)

PubMed Central

Rangus, Mojca; Mazaj, Matjaž; Dražić, Goran; Popova, Margarita; Tušar, Nataša Novak

2014-01-01

Iron-functionalized disordered mesoporous silica (FeKIL-2) is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs) from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS) and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM). We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05). From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1) the optimal concentration of stable isolated Fe3+ in the silica support; and (2) accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2) when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41). PMID:28788674

A modular continuous flow reactor system for the selective bio-oxidation of iron and precipitation of schwertmannite from mine-impacted waters.

PubMed

Hedrich, Sabrina; Johnson, D Barrie

2012-02-01

A novel modular bioremediation system which facilitates the selective removal of soluble iron from extremely acidic (pH ∼2) metal-rich wastewaters by ferrous iron oxidation and selective precipitation of the ferric iron produced is described. In the first of the three modules, rapid ferrous iron oxidation was mediated by the recently-characterized iron-oxidizing autotrophic acidophile, "Ferrovum myxofaciens", which grew as long "streamers" within the reactor. Over 90% of the iron present in influent test liquors containing 280mg/L iron was oxidized at a dilution rate of 0.41h(-1), in a proton-consuming reaction. The ferric iron-rich solutions produced were pumped into a second reactor where controlled addition of sodium hydroxide caused the water pH to increase to 3.5 and ferric iron to precipitate as the mineral schwertmannite. Addition of a flocculating agent promoted rapid aggregation and settling of the fine-grain schwertmannite particles. A third passive module (a packed-bed bioreactor, also inoculated with "Fv. myxofaciens") acted as a polishing reactor, lowering soluble iron concentrations in the processed water to <1mg/L. The system was highly effective in selectively removing iron from a synthetic acidic (pH 2.1) mine water that contained soluble aluminum, copper, manganese and zinc in addition to iron. Schwertmannite was again produced, with little or no co-precipitation of other metals. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

2017-08-01

Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O2 on ferrihydrite surfaces should include an electrochemical pathway, i.e., electron transfer (ET) in the Mn(II)-Conduction Band (CB)Ferrihydrite-O2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e., ET in the Mn(II)-Fe(II, III)-O2 complexes and direct ET in the Mn(II)-O2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments.

Iron oxide bands in the visible and near-infrared reflectance spectra of primitive asteroids

NASA Technical Reports Server (NTRS)

Jarvis, Kandy S.; Vilas, Faith; Gaffey, Michael J.

1993-01-01

High resolution reflectance spectra of primitive asteroids (C, P, and D class and associated subclasses) have commonly revealed an absorption feature centered at 0.7 microns attributed to an Fe(2+)-Fe(3+) charge transfer transition in iron oxides and/or oxidized iron in phyllosilicates. A smaller feature identified at 0.43 microns has been attributed to an Fe(3+) spin-forbidden transition in iron oxides. In the spectra of the two main-belt primitive asteroids 368 Haidea (D) and 877 Walkure (F), weak absorption features which were centered near the location of 0.60-0.65 microns and 0.80-0.90 microns prompted a search for features at these wavelengths and an attempt to identify their origin(s). The CCD reflectance spectra obtained between 1982-1992 were reviewed for similar absorption features located near these wavelengths. The spectra of asteroids in which these absorption features have been identified are shown. These spectra are plotted in order of increasing heliocentric distance. No division of the asteroids by class has been attempted here (although the absence of these features in the anhydrous S-class asteroids, many of which have presumably undergone full heating and differentiation should be noted). For this study, each spectrum was treated as a continuum with discrete absorption features superimposed on it. For each object, a linear least squares fit to the data points defined a simple linear continuum. The linear continuum was then divided into each spectrum, thus removing the sloped continuum and permitting the intercomparison of residual spectral features.

The nanophase iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

Invar alloys: information from the study of iron meteorites.

NASA Astrophysics Data System (ADS)

Goldstein, J. I.; Williams, D. B.; Zhang, J.; Clarke, R.

The iron meteorites were slow cooled (<108years) in their asteroidal bodies and are useful as indicators of the phase transformations which occur in Fe-Ni alloys. In the invar composition range, the iron meteorites contain a cloudy zone structure composed of an ordered tetrataenite phase and a surrounding honeycomb phase either of gamma or alpha phase. This structure is the result of a spinodal reaction below 350°C. The Santa Catharina iron meteorite has the typical invar composition of 36 wt% Ni and its structure is entirely cloudy zone although some of the honeycomb phase has been oxidized by terrestrial corrosion. Invar alloys would contain such a cloudy zone structure if more time was available for cooling. A higher temperature spinodal in the Fe-Ni phase diagram may be operative in invar alloys but has not been observed in the structure of the iron meteorites.

An empirical approach to predicting long term behavior of metal particle based recording media

NASA Technical Reports Server (NTRS)

Hadad, Allan S.

1992-01-01

Alpha iron particles used for magnetic recording are prepared through a series of dehydration and reduction steps of alpha-Fe2O3-H2O resulting in acicular, polycrystalline, body centered cubic (bcc) alpha-Fe particles that are single magnetic domains. Since fine iron particles are pyrophoric by nature, stabilization processes had to be developed in order for iron particles to be considered as a viable recording medium for long term archival (i.e., 25+ years) information storage. The primary means of establishing stability is through passivation or controlled oxidation of the iron particle's surface. A study was undertaken to examine the degradation in magnetic properties as a function of both temperature and humidity on silicon-containing iron particles between 50-120 C and 3-89 percent relative humidity. The methodology to which experimental data was collected and analyzed leading to predictive capability is discussed.

Oxidative Injury and Iron Redistribution Are Pathological Hallmarks of Marmoset Experimental Autoimmune Encephalomyelitis.

PubMed

Dunham, Jordon; Bauer, Jan; Campbell, Graham R; Mahad, Don J; van Driel, Nikki; van der Pol, Susanne M A; 't Hart, Bert A; Lassmann, Hans; Laman, Jon D; van Horssen, Jack; Kap, Yolanda S

2017-06-01

Oxidative damage and iron redistribution are associated with the pathogenesis and progression of multiple sclerosis (MS), but these aspects are not entirely replicated in rodent experimental autoimmune encephalomyelitis (EAE) models. Here, we report that oxidative burst and injury as well as redistribution of iron are hallmarks of the MS-like pathology in the EAE model in the common marmoset. Active lesions in the marmoset EAE brain display increased expression of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (p22phox, p47phox, and gp91phox) and inducible nitric oxide synthase immunoreactivity within lesions with active inflammation and demyelination, coinciding with enhanced expression of mitochondrial heat-shock protein 70 and superoxide dismutase 1 and 2. The EAE lesion-associated liberation of iron (due to loss of iron-containing myelin) was associated with altered expression of the iron metabolic markers FtH1, lactoferrin, hephaestin, and ceruloplasmin. The enhanced expression of oxidative damage markers in inflammatory lesions indicates that the enhanced antioxidant enzyme expression could not counteract reactive oxygen and nitrogen species-induced cellular damage, as is also observed in MS brains. This study demonstrates that oxidative injury and aberrant iron distribution are prominent pathological hallmarks of marmoset EAE thus making this model suitable for therapeutic intervention studies aimed at reducing oxidative stress and associated iron dysmetabolism. © 2017 American Association of Neuropathologists, Inc. All rights reserved.

Mineral Magnetic Properties of Partially Oxidized Siderite

NASA Astrophysics Data System (ADS)

Dekkers, M. J.; Hanckmann, W. J. F.; Spassov, S.; Behrends, T.

2017-12-01

Siderite (FeCO3) is an important mineral in iron redox cycling in the subsurface. It is often characterized geochemically by means of various sequential extraction schemes. However, a mineralogical siderite determination remains rather tedious, particularly when dealing with trace amounts and very fine particles, often the rule in soils and sediments. Here we explore the suitability of the very sensitive magnetic methods to this end, exploiting siderite's magnetic properties at low temperature. The basic magnetic properties of siderite are surprisingly poorly characterized. To contribute to this issue, we have synthesized siderite with varying amounts of ferric iron in a chemostat, next to the magnetic characterization of several siderites from mineral collections. By slowly adding ferrous iron perchlorate to a carbonate solution the synthesis could be tweaked in order to deliver products as crystalline as possible. Synthesis products were verified with XRD; at pH below 7 siderite was the dominant phase, at higher pH the mineral chukanovite (Fe2(OH)2CO3) was found. The degree of oxidation was measured wet-chemically with the ferrozine method. Samples appeared to be oxidized between 1 and 80%, most samples between 1 and 6%. The sequence of low temperature magnetic measurements (on an MPMS3 system) included 1) cooling in a field of 15 mT to 5 K, 2) warming of a 5 T IRM given at 5 K in zero field to 300 K, 3) cooling in a field of 5 T to 5 K, and 4) warming of the field-cooled 5 T IRM in zero field to 300 K. For mineral collection siderite also hysteresis loops were determined at several temperatures to determine the exchange bias field. Conform literature data siderite was found to have a magnetic ordering temperature of 38 K. Oxidation appears to smear out the remanence warming curves while also shifting the ordering temperature upward. Specific magnetic moments were found to vary distinctly, being both lower and higher than reference values. We relate this tentatively to grain size effects that play up since siderite is an antiferromagnet and far from saturation in a 5 T field. Standard addition experiments indicated that one per mil siderite can be traced rock-magnetically, enabling a check on sequential extraction schemes designed to allocate iron to several redox-sensitive pools in natural samples.

Characterization of tetraethylene glycol passivated iron nanoparticles

NASA Astrophysics Data System (ADS)

Nunes, Eloiza da Silva; Viali, Wesley Renato; da Silva, Sebastião William; Coaquira, José Antonio Huamaní; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Morais, Paulo César; Jafelicci Júnior, Miguel

2014-10-01

The present study describes the synthesis and characterization of iron@iron oxide nanoparticles produced by passivation of metallic iron in tetraethylene glycol media. Structural and chemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mössbauer spectroscopy. Pomegranate-like core@shell nanoparticulate material in the size range of 90-120 nm was obtained. According to quantitative phase analysis using Rietveld structure refinement the synthesized iron oxide was identified as magnetite (Fe3O4) whereas the iron to magnetite mass fractions was found to be 47:53. These findings are in good agreement with the data obtained from Mössbauer and thermal gravimetric analysis (TGA). The XPS data revealed the presence of a surface organic layer with higher hydrocarbon content, possibly due to the tetraethylene glycol thermal degradation correlated with iron oxidation. The room-temperature (300 K) saturation magnetization measured for the as-synthesized iron and for the iron-iron oxide were 145 emu g-1 and 131 emu g-1, respectively. The measured saturation magnetizations are in good agreement with data obtained from TEM, XRD and Mössbauer spectroscopy.

Phenolic Wastewater Treatment Alternatives.

DTIC Science & Technology

1980-06-01

15 Potassium Permanganate ................ 19 Iron (VI) Ferrate ..................... 22 Catalytic Oxidation ..................... 22...carbon dioxide, potassium hydroxide, and manganese dioxide which were readily handled by the existing system. d. Iron (VI) Ferrate Ferrate is iron in...the following systems/processes: Granular Activated Carbon (GAC) adsorption, ozone oxidation, hydrogen peroxide oxidation, potassium permanganate

Prediction of iron oxide contents using diffuse reflectance spectroscopy

NASA Astrophysics Data System (ADS)

Marques, José, Jr.; Arantes Camargo, Livia

2015-04-01

Determining soil iron oxides using conventional analysis is relatively unfeasible when large areas are mapped, with the aim of characterizing spatial variability. Diffuse reflectance spectroscopy (DRS) is rapid, less expensive, non-destructive and sometimes more accurate than conventional analysis. Furthermore, this technique allows the simultaneous characterization of many soil attributes with agronomic and environmental relevance. This study aims to assess the DRS capability to predict iron oxides content -hematite and goethite - , characterizing their spatial variability in soils of Brazil. Soil samples collected from an 800-hectare area were scanned in the visible and near-infrared spectral range. Moreover, chemometric calibration was obtained through partial least-squares regression (PLSR). Then, spatial distribution maps of the attributes were constructed using predicted values from calibrated models through geostatistical methods. The studied area presented soils with varied contents of iron oxides as examples for the Oxisols and Entisols. In the spectra of each soil is observed that the reflectance decreases with the content of iron oxides present in the soil. In soils with a high content of iron oxides can be observed more pronounced concavities between 380 and 1100 nm which are characteristic of the presence of these oxides. In soils with higher reflectance it were observed concavity characteristics due to the presence of kaolinite, in agreement with the low iron contents of those soils. The best accuracy of prediction models [residual prediction deviation (RPD) = 1.7] was obtained for goethite within the visible region (380-800 nm), and for hematite (RPD = 2.0) within the visible near infrared (380-2300 nm). The maps of goethite and hematite predicted showed the spatial distribution pattern similar to the maps of clay and iron extracted by dithionite-citrate-bicarbonate, being consistent with the iron oxide contents of soils present in the study area. These results confirm the value of DRS in the mapping of iron oxides in large areas at detailed scale.

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.

From Río Tinto to Mars: the terrestrial and extraterrestrial ecology of acidophiles.

PubMed

Amils, R; González-Toril, E; Aguilera, A; Rodríguez, N; Fernández-Remolar, D; Gómez, F; García-Moyano, A; Malki, M; Oggerin, M; Sánchez-Andrea, I; Sanz, J L

2011-01-01

The recent geomicrobiological characterization of Río Tinto, Iberian Pyrite Belt (IPB), has proven the importance of the iron cycle, not only in generating the extreme conditions of the habitat (low pH, high concentration of toxic heavy metals) but also in maintaining the high level of microbial diversity, both prokaryotic and eukaryotic, detected in the water column and the sediments. The extreme conditions of the Tinto basin are not the product of industrial contamination but the consequence of the presence of an underground bioreactor that obtains its energy from the massive sulfide minerals of the IPB. To test this hypothesis, a drilling project was carried out to intersect ground waters that interact with the mineral ore in order to provide evidence of subsurface microbial activities and the potential resources to support these activities. The oxidants that drive the system appear to come from the rock matrix, contradicting conventional acid mine drainage models. These resources need only groundwater to launch microbial metabolism. There are several similarities between the vast deposits of sulfates and iron oxides on Mars and the main sulfide-containing iron bioleaching products found in the Tinto. Firstly, the short-lived methane detected both in Mars' atmosphere and in the sediments and subsurface of the IPB and secondly, the abundance of iron, common to both. The physicochemical properties of iron make it a source of energy, a shield against radiation and oxidative stress as well as a natural pH controller. These similarities have led to Río Tinto's status as a Mars terrestrial analogue. Copyright © 2011 Elsevier Inc. All rights reserved.

Modulation of the antioxidative response of Spartina densiflora against iron exposure.

PubMed

Martínez Domínguez, David; Torronteras Santiago, Rafael; Córdoba García, Francisco

2009-06-01

Spartina densiflora, an invader cordgrass living in polluted salt marshes of the Odiel estuary (SW Spain), was collected and cultured under controlled laboratory conditions. After acclimation to non-polluted soils for 28 days, both metabolites and enzymes activities used as indicators of oxidative stress were reduced significantly. Then, plants were exposed to 500 and 1000 ppm Fe-ethylenediamine-N,N'-2-hydroxyphenyl acetic acid (EDDHA) for 28 days. Our data demonstrate that iron content in leaves was enhanced by iron exposure. This iron increase caused an enhancement in the concentration of H2O2, hydroperoxides and lipid peroxidation, and a decrease in chlorophyll levels. Thus, iron exposure led to oxidative stress conditions. However, oxidative indicators stabilised after first 2 weeks of exposure, although the highest iron levels in leaves were reached at the end of treatments. Iron exposure induced an enhancement of catalase, ascorbate peroxidase and guaiacol peroxidase activities, together with an increase in total and oxidised ascorbate. This response may be defensive against oxidative stress and thus help to explain why cell oxidative damages were stabilised. Thus, by using a sensitive long-time protocol, iron-dependent oxidative damages may be controlled and even reverted successfully by the activation of the antioxidative defences of S. densiflora. This efficient antioxidative system, rapidly modulated in response to excess iron and other environmental stressors, may account for S. densiflora's successful adaptation to stress conditions in its habitat.

Impact of iron and vitamin C-containing supplements on preterm human milk: in vitro.

PubMed

Friel, James K; Diehl-Jones, William L; Suh, Miyoung; Tsopmo, Apollinaire; Shirwadkar, Vaibhav P

2007-05-15

Stress due to reactive oxygen species (ROS) may lead to neonatal diseases, such as necrotizing enterocolitis and respiratory distress. Enteral supplements for premature infants (PREM) added to human milk (HM) to increase nutrient content may induce lipid oxidation due to free radical formation via Fenton chemistry. We hypothesized that ferrous iron and vitamin C-containing supplements added to HM in vitro cause oxidation of milk fats, affect intracellular redox balance, and induce DNA damage. Lipid peroxidation in HM was measured by FOX-2 and TBARS assays; fatty acid composition of supplemented HM was measured by gas chromatography. Two cell culture bioassays were used for assessing either intracellular oxidative stress or DNA damage: the former involved Caco-2BBe cells, a secondary differentiated cell line, and the latter utilized FHS-74 Int cells, a primary fetal small intestinal culture. Lipid oxidation products of HM increased after the addition of iron alone, iron and vitamin C, or iron and a vitamin C-containing supplement (Trivisol, TVS). A reduced content of mono and polyunsaturated fatty acids in HM was also observed. Iron, not iron+vitamin C, but iron+TVS induced significant intracellular oxidative stress in FHS-74 Int cells. In contrast, iron, either alone or in combination with TVS or vitamin C, increased DNA damage in Caco-2BBE cells. Iron supplementation may increase oxidative stress in PREM infants and should be given separately from vitamin C-containing supplements.

Isolation of iron bacteria from terrestrial and aquatic environments

NASA Astrophysics Data System (ADS)

Schmidt, Bertram; Szewzyk, Ulrich

2010-05-01

Bacteria, which are capable of iron oxidation or at least iron deposition are widely distributed in environments where zones of dissolved ferrous iron and oxygen gradients are overlapping [1]. They take part in the biological cycling of iron and influence other cycles of elements for example carbon [2]. Manganese can be used for similar metabolic purposes as iron, because it can be biologically oxidized by chemolithotrophs or can be reduced by respirating bacteria as well [3, 4]. Bacterial activity is responsible for the accumulation of ferric iron compounds in their surroundings. The formation of bog ore is a well known example for a soil horizon, with an extreme enrichment of biogenic ferric iron [5]. We focused on the isolation of neutrophilic iron bacteria and bacteria capable of manganese oxidation. We used samples from Tierra del Fuego (Argentina) the National Park "Unteres Odertal" (Germany) and Berlin ground water wells. Microscopic examination of the samples revealed a considerable diversity of iron encrusted structures of bacterial origin. Most of these morphologic types are already well known. The taxonomic classification of many of these organisms is based on morphologic features and is not reliable compared to recent methods of molecular biology. That is mainly due to the fact, that most of these bacteria are hardly culturable or do not show their characteristic morphologic features under culture conditions. We established a collection of more than 300 iron depositing strains. Phylogenetic analyses showed that we have many yet uncultured strains in pure culture. We obtained many isolates which form distinct branches within long known iron bacteria groups like the Sphaerotilus-Leptothrix cluster. But some of the strains belong to groups, which have not yet been associated with iron oxidation activity. The strains deposit high amounts of oxidized iron and manganese compounds under laboratory conditions. However it is unclear if these precipitations are due to biological oxidation or biological deposition of chemically oxidized iron. We examined the morphologic characteristics of selected isolates under near-natural conditions to assign them to morphologic structures which occur in native samples. Our aim for the future is to describe several strains. References: [1] Weber, K. A. ; Achenbach, L. A. ; Coates, J. D. : Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. In: Nature Reviews Microbiology 4 (2006) 752-764 [2] Van Capellen, P. ; Wang Y. : Cycling of iron and manganese in surface sediments: a general theory for the coupled transport and reaction of carbon, oxygen, nitrogen, sulfur, iron and manganese. In: American Journal of Science 296 (1996) 197-243 [3] Tebo, B. M. ; Bargar, J. R. ; Clement, B. G. ; Dick, G. J. ; Murray, K. J. ; Parker, D. Verity R. ; Webb, S. M. : Biogenic manganese oxides: properties and mechanisms of formation. In: Annual Reviews Earth Planet Science 32 (2004) 287-328 [4] Erlich, H. L. : Manganese oxide reduction as a form of anaerobic respiration. In: Geomicrobiology Journal 5 (1987) 423-431 [5] Ghiorse W. C. : Biology of iron- and manganese-depositing bacteria. In: Annual Reviews 38 (1984) 515-550

Iron metabolism: current facts and future directions

PubMed Central

Tandara, Leida; Salamunic, Ilza

2012-01-01

Iron metabolism has been intensively examined over the last decade and there are many new players in this field which are worth to be introduced. Since its discovery many studies confirmed role of liver hormone hepcidin as key regulator of iron metabolism and pointed out liver as the central organ of system iron homeostasis. Liver cells receive multiple signals related to iron balance and respond by transcriptional regulation of hepcidin expression. This liver hormone is negative regulator of iron metabolism that represses iron efflux from macrophages, hepatocytes and enterocytes by its binding to iron export protein ferroportin. Ferroportin degradation leads to cellular iron retention and decreased iron availability. At level of a cell IRE/IRP (iron responsive elements/iron responsive proteins) system allows tight regulation of iron assimilation that prevents an excess of free intracellular iron which could lead to oxidative stress and damage of DNA, proteins and lipid membranes by ROS (reactive oxygen species). At the same time IRE/IRP system provides sufficient iron in order to meet the metabolic needs. Recently a significant progress in understanding of iron metabolism has been made and new molecular participants have been characterized. Article gives an overview of the current understanding of iron metabolism: absorption, distribution, cellular uptake, release, and storage. We also discuss mechanisms underlying systemic and cellular iron regulation with emphasis on central regulatory hormone hepcidin. PMID:23092063

Arsenic mobilization and immobilization in paddy soils

NASA Astrophysics Data System (ADS)

Kappler, A.; Hohmann, C.; Zhu, Y. G.; Morin, G.

2010-05-01

Arsenic is oftentimes of geogenic origin and in many cases bound to iron(III) minerals. Iron(III)-reducing bacteria can harvest energy by coupling the oxidation of organic or inorganic electron donors to the reduction of Fe(III). This process leads either to dissolution of Fe(III)-containing minerals and thus to a release of the arsenic into the environment or to secondary Fe-mineral formation and immobilisation of arsenic. Additionally, aerobic and anaerobic iron(II)-oxidizing bacteria have the potential to co-precipitate or sorb arsenic during iron(II) oxidation at neutral pH that is usually followed by iron(III) mineral precipitation. We are currently investigating arsenic immobilization by Fe(III)-reducing bacteria and arsenic co-precipitation and immobilization by anaerobic iron(II)-oxidizing bacteria in batch, microcosm and rice pot experiments. Co-precipitation batch experiments with pure cultures of nitrate-dependent Fe(II)-oxidizing bacteria are used to quantify the amount of arsenic that can be immobilized during microbial iron mineral precipitation, to identify the minerals formed and to analyze the arsenic binding environment in the precipitates. Microcosm and rice pot experiments are set-up with arsenic-contaminated rice paddy soil. The microorganisms (either the native microbial population or the soil amended with the nitrate-dependent iron(II)-oxidizing Acidovorax sp. strain BoFeN1) are stimulated either with iron(II), nitrate, or oxygen. Dissolved and solid-phase arsenic and iron are quantified. Iron and arsenic speciation and redox state in batch and microcosm experiments are determined by LC-ICP-MS and synchrotron-based methods (EXAFS, XANES).

Bmp6 Regulates Retinal Iron Homeostasis and Has Altered Expression in Age-Related Macular Degeneration

PubMed Central

Hadziahmetovic, Majda; Song, Ying; Wolkow, Natalie; Iacovelli, Jared; Kautz, Leon; Roth, Marie-Paule; Dunaief, Joshua L.

2011-01-01

Iron-induced oxidative stress causes hereditary macular degeneration in patients with aceruloplasminemia. Similarly, retinal iron accumulation in age-related macular degeneration (AMD) may exacerbate the disease. The cause of retinal iron accumulation in AMD is poorly understood. Given that bone morphogenetic protein 6 (Bmp6) is a major regulator of systemic iron, we examined the role of Bmp6 in retinal iron regulation and in AMD pathogenesis. Bmp6 was detected in the retinal pigment epithelium (RPE), a major site of pathology in AMD. In cultured RPE cells, Bmp6 was down-regulated by oxidative stress and up-regulated by iron. Intraocular Bmp6 protein injection in mice up-regulated retinal hepcidin, an iron regulatory hormone, and altered retinal labile iron levels. Bmp6−/− mice had age-dependent retinal iron accumulation and degeneration. Postmortem RPE from patients with early AMD exhibited decreased Bmp6 levels. Because oxidative stress is associated with AMD pathogenesis and down-regulates Bmp6 in cultured RPE cells, the diminished Bmp6 levels observed in RPE cells in early AMD may contribute to iron build-up in AMD. This may in turn propagate a vicious cycle of oxidative stress and iron accumulation, exacerbating AMD and other diseases with hereditary or acquired iron excess. PMID:21703414

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.1200 - Synthetic iron oxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.1200 Section 73.1200 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1200 Synthetic iron oxide. (a) Identity. (1) The...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

21 CFR 73.2250 - Iron oxides.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR... per million. (c) Uses and restrictions. Iron oxides are safe for use in coloring cosmetics generally...

Impact of Microcystis aeruginosa Exudate on the Formation and Reactivity of Iron Oxide Particles Following Fe(II) and Fe(III) Addition.

PubMed

Garg, Shikha; Wang, Kai; Waite, T David

2017-05-16

Impact of the organic exudate secreted by a toxic strain of Microcystis aeruginosa on the formation, aggregation, and reactivity of iron oxides that are formed on addition of Fe(II) and Fe(III) salts to a solution of the exudate is investigated in this study. The exudate has a stabilizing effect on the particles formed with decreased aggregation rate and increased critical coagulant concentration required for diffusion-limited aggregation to occur. These results suggest that the presence of algal exudates from Microcystis aeruginosa may significantly influence particle aggregation both in natural water bodies where Fe(II) oxidation results in oxide formation and in water treatment where Fe(III) salts are commonly added to aid particle growth and contaminant capture. The exudate also affects the reactivity of iron oxide particles formed with exudate coated particles undergoing faster dissolution than bare iron oxide particles. This has implications to iron availability, especially where algae procure iron via dissolution of iron oxide particles as a result of either reaction with reducing moieties, light-mediated ligand to metal charge transfer and/or reaction with siderophores. The increased reactivity of exudate coated particles is attributed, for the most part, to the smaller size of these particles, higher surface area and increased accessibility of surface sites.

Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications

PubMed Central

Wu, Wei; Wu, Zhaohui; Yu, Taekyung; Jiang, Changzhong; Kim, Woo-Sik

2015-01-01

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed. PMID:27877761

Terrestrial Fe-oxide Concretions and Mars Blueberries: Comparisons of Similar Advective and Diffusive Chemical Infiltration Reaction Mechanisms

NASA Astrophysics Data System (ADS)

Park, A. J.; Chan, M. A.

2006-12-01

Abundant iron oxide concretions occurring in Navajo Sandstone of southern Utah and those discovered at Meridiani Planum, Mars share many common observable physical traits such as their spheriodal shapes, occurrence, and distribution patterns in sediments. Terrestrial concretions are products of interaction between oxygen-rich aquifer water and basin-derived reducing (iron-rich) water. Water-rock interaction simulations show that diffusion of oxygen and iron supplied by slow-moving water is a reasonable mechanism for producing observed concretion patterns. In short, southern Utah iron oxide concretions are results of Liesegang-type diffusive infiltration reactions in sediments. We propose that the formation of blueberry hematite concretions in Mars sediments followed a similar diagenetic mechanism where iron was derived from the alteration of volcanic substrate and oxygen was provided by the early Martian atmosphere. Although the terrestrial analog differs in the original host rock composition, both the terrestrial and Mars iron-oxide precipitation mechanisms utilize iron and oxygen interactions in sedimentary host rock with diffusive infiltration of solutes from two opposite sources. For the terrestrial model, slow advection of iron-rich water is an important factor that allowed pervasive and in places massive precipitation of iron-oxide concretions. In Mars, evaporative flux of water at the top of the sediment column may have produced a slow advective mass-transfer mechanism that provided a steady source and the right quantity of iron. The similarities of the terrestrial and Martian systems are demonstrated using a water-rock interaction simulator Sym.8, initially in one-dimensional systems. Boundary conditions such as oxygen content of water, partial pressure of oxygen, and supply rate of iron were varied. The results demonstrate the importance of slow advection of water and diffusive processes for producing diagenetic iron oxide concretions.

Interaction of fluorescent sensor with superparamagnetic iron oxide nanoparticles.

PubMed

Karunakaran, Chockalingam; Jayabharathi, Jayaraman; Sathishkumar, Ramalingam; Jayamoorthy, Karunamoorthy

2013-06-01

To sense superparamagnetic iron oxides (Fe2O3 and Fe3O4) nanocrystals a sensitive bioactive phenanthroimidazole based fluorescent molecule, 2-(4-fluorophenyl)-1-phenyl-1H-phenanthro [9,10-d] imidazole has been designed and synthesized. Electronic spectral studies show that phenanthroimidazole is bound to the surface of iron oxide semiconductors. Fluorescent enhancement has been explained on the basis of photo-induced electron transfer (PET) mechanism and apparent binding constants have been deduced. Binding of phenanthroimidazole with iron oxide nanoparticles lowers the HOMO and LUMO energy levels of phenanthroimidazole molecule. Chemical affinity between the nitrogen atom of the phenanthroimidazole and Fe(2+) and Fe(3+) ions on the surface of the nano-oxide may result in strong binding of the phenanthroimidazole derivative with the nanoparticles. The electron injection from the photoexcited phenanthroimidazole to the iron oxides conduction band explains the enhanced fluorescence. Copyright © 2013 Elsevier B.V. All rights reserved.

Magnetite-hematite transformation: correlation between natural and synthetic features

NASA Astrophysics Data System (ADS)

Barbosa, Paola F.; Lagoeiro, Leonardo; Scholz, Ricardo; Graça, Leonardo M.; Mohallem, Nelcy

2015-06-01

The iron-oxide system can be used as a marker of oxidized and reduced conditions in closed systems. However, natural rocks with iron oxide minerals also exhibit such reactions, although the natural system is typically open. To understand the behaviour of this natural system, some similarities were investigated, in terms of crystallographic textures, between the microstructures of two systems: natural open system and synthetic closed system of iron oxide phase transformation. Particular cases of phase transformation in iron oxide minerals, described as natural reactions of magnetite to hematite and synthetic reactions of hematite to magnetite, were chosen. It is observed, in both scenarios, that the transformation obeys the topotaxial and epitaxial relationship, which are well described for the iron oxide system. However, in natural open systems, the precipitation of a new phase during the in situ transformation modifies the microstructures and must be taken into account as an important factor to describe them.

Ferroxidase-Mediated Iron Oxide Biomineralization: Novel Pathways to Multifunctional Nanoparticles.

PubMed

Zeth, Kornelius; Hoiczyk, Egbert; Okuda, Mitsuhiro

2016-02-01

Iron oxide biomineralization occurs in all living organisms and typically involves protein compartments ranging from 5 to 100nm in size. The smallest iron-oxo particles are formed inside dodecameric Dps protein cages, while the structurally related ferritin compartments consist of twice as many identical protein subunits. The largest known compartments are encapsulins, icosahedra made of up to 180 protein subunits that harbor additional ferritin-like proteins in their interior. The formation of iron-oxo particles in all these compartments requires a series of steps including recruitment of iron, translocation, oxidation, nucleation, and storage, that are mediated by ferroxidase centers. Thus, compartmentalized iron oxide biomineralization yields uniform nanoparticles strictly determined by the sizes of the compartments, allowing customization for highly diverse nanotechnological applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxidative Stress and the Homeodynamics of Iron Metabolism

PubMed Central

Bresgen, Nikolaus; Eckl, Peter M.

2015-01-01

Iron and oxygen share a delicate partnership since both are indispensable for survival, but if the partnership becomes inadequate, this may rapidly terminate life. Virtually all cell components are directly or indirectly affected by cellular iron metabolism, which represents a complex, redox-based machinery that is controlled by, and essential to, metabolic requirements. Under conditions of increased oxidative stress—i.e., enhanced formation of reactive oxygen species (ROS)—however, this machinery may turn into a potential threat, the continued requirement for iron promoting adverse reactions such as the iron/H2O2-based formation of hydroxyl radicals, which exacerbate the initial pro-oxidant condition. This review will discuss the multifaceted homeodynamics of cellular iron management under normal conditions as well as in the context of oxidative stress. PMID:25970586

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

Experimental constrain of hydrogen production during early serpentinization stages

NASA Astrophysics Data System (ADS)

Clément, M.; Munoz, M.; Vidal, O.; Parra, T.

2009-04-01

Hydrothermal alteration of mantellic peridotites and ultramafic rocks along axial valleys of low spread oceanic ridges plays a key role in different fundamental domains like, 1) energetic gaz production (H2 and hydrocarbons) representing a potential source of energy for future generations, 2) formation of organic pre-biotic molecules in potential relation with the origin of life. Moreover, such complex volcanic-related alteration processes play fundamental role in economic geology, being widely associated to important polymetallic sulphides ore deposits. Recent researches proposed an initial hydrogen production due to the integration of ferric iron in Fe,Mg-serpentine. To better understand the early stages of hydrogen production, a series of natural peridotite rocks have been experimentally exposed to hydrothermal conditions, up to 300°C, 300 bars during different time scales. Experiments have been performed in using autoclaves with a sampling gas system. A systematic mineralogical characterization of the new products was carried out using classical spectroscopic tools. In particular, we focused on the iron behaviour using a redox and structural micro-XANES investigation. Redox information has been accurately derived from the pre-peak features previously calibrated from model compounds, while structural information about short and medium range order around iron has been extracted from the XANES region of the spectra, based both on experimental standards and ab-initio theoretical calculations. Two processes of oxidation emerged. Before two month experiment duration, serpentine displays a not negligible oxidation of ferrous iron in his structure (up to 60%), while after two months, iron oxides and hydroxides appear in the system. These results seem to correspond to natural observations. The iron coordination decreases linearly with time. It means that iron also integrates the serpentine tetrahedral sites. Moreover, high resolution µ-XAS maps on experimental samples were collected on the iron K-edge (7712 eV). These maps give valuable information concerning both kinetic of mineral phases transformation and spatial speciation of iron through the altered part of the samples. Finally, these results allow us to define a non linear model of "Fe3+ in serpentine vs hydrogen production" as a function of time.

Gold and gold-iron oxide magnetic glyconanoparticles: synthesis, characterization and magnetic properties.

PubMed

de la Fuente, Jesús M; Alcántara, David; Eaton, Peter; Crespo, Patricia; Rojas, Teresa C; Fernandez, Asunción; Hernando, Antonio; Penadés, Soledad

2006-07-06

The preparation, characterization and the magnetic properties of gold and gold-iron oxide glyconanoparticles (GNPs) are described. Glyconanoparticles were prepared in a single step procedure in the presence of aqueous solution of thiol functionalized neoglycoconjugates and either gold salts or both gold and iron salts. Neoglycoconjugates of lactose and maltose disaccharides with different linkers were used. Iron-free gold or gold-iron oxide GNPs with controlled gold-iron ratios were obtained. The average core-size diameters are in the range of 1.5-2.5 nm. The GNPs are fully characterized by (1)H NMR spectrometry, transmission electron microscopy (TEM), and UV-vis and X-ray absorption (XAS) spectroscopies. Inductive plasma-atomic emission spectrometry (ICP) and elemental analysis gave the average number of neoglycoconjugates per cluster. The magnetic properties were measured in a SQUID magnetometer. The most remarkable results was the observation of a permanent magnetism up to room temperature in the iron-free gold GNPs, that was not present in the corresponding gold-iron oxide GNPs.

Toward a Mechanistic Understanding of Anaerobic Nitrate-Dependent Iron Oxidation: Balancing Electron Uptake and Detoxification

PubMed Central

Carlson, Hans K.; Clark, Iain C.; Melnyk, Ryan A.; Coates, John D.

2011-01-01

The anaerobic oxidation of Fe(II) by subsurface microorganisms is an important part of biogeochemical cycling in the environment, but the biochemical mechanisms used to couple iron oxidation to nitrate respiration are not well understood. Based on our own work and the evidence available in the literature, we propose a mechanistic model for anaerobic nitrate-dependent iron oxidation. We suggest that anaerobic iron-oxidizing microorganisms likely exist along a continuum including: (1) bacteria that inadvertently oxidize Fe(II) by abiotic or biotic reactions with enzymes or chemical intermediates in their metabolic pathways (e.g., denitrification) and suffer from toxicity or energetic penalty, (2) Fe(II) tolerant bacteria that gain little or no growth benefit from iron oxidation but can manage the toxic reactions, and (3) bacteria that efficiently accept electrons from Fe(II) to gain a growth advantage while preventing or mitigating the toxic reactions. Predictions of the proposed model are highlighted and experimental approaches are discussed. PMID:22363331

Investigation of energy gene expressions and community structures of free and attached acidophilic bacteria in chalcopyrite bioleaching.

PubMed

Zhu, Jianyu; Jiao, Weifeng; Li, Qian; Liu, Xueduan; Qin, Wenqing; Qiu, Guanzhou; Hu, Yuehua; Chai, Liyuan

2012-12-01

In order to better understand the bioleaching mechanism, expression of genes involved in energy conservation and community structure of free and attached acidophilic bacteria in chalcopyrite bioleaching were investigated. Using quantitative real-time PCR, we studied the expression of genes involved in energy conservation in free and attached Acidithiobacillus ferrooxidans during bioleaching of chalcopyrite. Sulfur oxidation genes of attached A. ferrooxidans were up-regulated while ferrous iron oxidation genes were down-regulated compared with free A. ferrooxidans in the solution. The up-regulation may be induced by elemental sulfur on the mineral surface. This conclusion was supported by the results of HPLC analysis. Sulfur-oxidizing Acidithiobacillus thiooxidans and ferrous-oxidizing Leptospirillum ferrooxidans were the members of the mixed culture in chalcopyrite bioleaching. Study of the community structure of free and attached bacteria showed that A. thiooxidans dominated the attached bacteria while L. ferrooxidans dominated the free bacteria. With respect to available energy sources during bioleaching of chalcopyrite, sulfur-oxidizers tend to be on the mineral surfaces whereas ferrous iron-oxidizers tend to be suspended in the aqueous phase. Taken together, these results indicate that the main role of attached acidophilic bacteria was to oxidize elemental sulfur and dissolution of chalcopyrite involved chiefly an indirect bioleaching mechanism.

Magnetic analysis of commercial hematite, magnetite, and their mixtures

NASA Astrophysics Data System (ADS)

Ahmadzadeh, Mostafa; Romero, Camila; McCloy, John

2018-05-01

Magnetic techniques are suitable to detect iron oxides even in trace concentrations. However, since several iron oxides may be simultaneously present in natural and synthetic samples, mixtures of magnetic particles and magnetic interactions between grains can complicate magnetic signatures. Among the iron oxide minerals, hematite (α-Fe2O3) and magnetite (Fe3O4) are the most common. In this work, different commercial hematite powders, normally used as Fe precursor in laboratory synthesis of Fe-containing oxides, were characterized using X-ray diffractometry (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometry (VSM). The effects of different concentrations of the hematite and magnetite on the magnetic properties of a set of mixtures (from 1 to 10 wt% magnetite) were then investigated by measuring the hysteresis loops, first order reversal curves (FORCs), thermal demagnetization, and isothermal remanent magnetization (IRM) curves. The three commercial hematite powders presented different magnetic behaviors mostly due to the effects of particle size. The magnetic results of mixtures reveal that it is very difficult to identify hematite magnetic signals by means of hysteresis loops, FORCs, or thermal demagnetization when even a small amount of magnetite (>5 wt%) is present due to magnetite's high specific magnetization. However, IRM was found to be a sensitive method to determine the presence of hematite when magnetite is simultaneously present as high as 10 wt%.

Evaluation of the effect of sulfate, alkalinity and disinfector on iron release of iron pipe and iron corrosion scale characteristics under water quality changing condition using response surface methodology

NASA Astrophysics Data System (ADS)

Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan

2018-02-01

The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.

Arsenic Mobilization Influenced By Iron Reduction And Sulfidogenesis Under Dynamic Flow

NASA Astrophysics Data System (ADS)

Kocar, B. D.; Stewart, B. D.; Herbel, M.; Fendorf, S.

2004-12-01

Sulfidogenesis and iron reduction are ubiquitous processes that occur in a variety of anoxic subsurface and surface environments, which profoundly impact the cycling of arsenic. Of the iron (hydr)oxides, ferrihydrite possesses one of the highest capacities to retain arsenic, and is globally distributed within soils and sediments. Upon dissimilatory iron reduction, ferrihydrite may transform to lower surface area minerals, such as goethite and magnetite, which decreases arsenic retention, thus enhancing its transport. Here we examine how arsenic retained on ferrihydrite is mobilized under dynamic flow in the presence of Sulfurosprillum barnesii strain SES-3, a bacteria capable of reducing both As(V) and Fe(III). Ferrihydrite coated sands, loaded with 150 mg kg-1 As(V), were inoculated with S. barnesii, packed into a column and reacted with a synthetic groundwater solution. Within several days after initiation of flow, the concentration of arsenic in the column effluent increased dramatically coincident with the mineralogical transformation of ferrihydrite and As(V) reduction to As(III). Following the initial pulse of arsenic, effluent concentration then declined to less than 10 μ M. Thus, arsenic release into the aqueous phase is contingent upon the incongruent reduction of As(V) and Fe(III) as mediated by biological activity. Reaction of abiotically or biotically generated dissolved sulfide with iron (hydr)oxides may have a dramatic influence on the fate of arsenic within surface and subsurface environments. Accordingly, we examined the reaction of dissolved bisulfide and iron (hydr)oxide complexed with arsenic in both batch and column systems. Low ratios of sulfide to iron in batch reaction systems result in the formation of elemental sulfur and concomitant arsenic release from the iron (hydr)oxide surface. High sulfide to iron ratios, in contrast, appear to favor the formation of iron and arsenic sulfides. Our findings demonstrate that iron (hydr)oxides may quench reactions between sulfide and constituents sorbed to iron (hydr)oxide surfaces, forming elemental sulfur as opposed to sulfide-arsenic complexes. In addition, reductive transformation of iron (hydr)oxide by dissolved sulfide may release sorbed constituents. Hence, moderate to low concentrations of dissolved sulfide in association with iron (hydr)oxides may inhibit sequestration of important contaminants that are attenuated by Fe(III) and/or S(-II) bearing phases.

Iron oxide nanoparticles supported on ultradispersed diamond powders: Effect of the preparation procedure

NASA Astrophysics Data System (ADS)

Dimitrov, Momtchil; Ivanova, Ljubomira; Paneva, Daniela; Tsoncheva, Tanya; Stavrev, Stavry; Mitov, Ivan; Minchev, Christo

2009-01-01

The state of the iron oxide nanoparticles, supported on ultradispersed diamond (UDD) powders is studied by X-ray diffraction, nitrogen physisorption, temperature-programmed reduction, FTIR and Mössbauer spectroscopy. Methanol decomposition to hydrogen and CO is used as a catalytic test. The peculiarities of the iron oxide species strongly depend on the detonation procedure used for the UDD powders preparation as well as on the iron modification procedure.

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched glasses from different temperatures, when possible, using wet-chemical analysis (i.e., K-dichromate potentiometry). Both datasets agree reasonably well (within 10 %). References: Wilke et al. (2004) Chemical Geology, 213, 71-87.

Process for the synthesis of iron powder

DOEpatents

Not Available

1982-03-06

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Process for the synthesis of iron powder

DOEpatents

Welbon, William W.

1983-01-01

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder.

Effect of bicarbonate on iron-mediated oxidation of low-density lipoprotein

NASA Astrophysics Data System (ADS)

Arai, Hirofumi; Berlett, Barbara S.; Chock, P. Boon; Stadtman, Earl R.

2005-07-01

Oxidation of low-density lipoprotein (LDL) may play an important role in atherosclerosis. We studied the effects of bicarbonate/CO2 and phosphate buffer systems on metal ion-catalyzed oxidation of LDL to malondialdehyde (MDA) and to protein carbonyl and MetO derivatives. Our results revealed that LDL oxidation in mixtures containing free iron or heme derivatives was much greater in bicarbonate/CO2 compared with phosphate buffer. However, when copper was substituted for iron in these mixtures, the rate of LDL oxidation in both buffers was similar. Iron-catalyzed oxidation of LDL was highly sensitive to inhibition by phosphate. Presence of 0.3-0.5 mM phosphate, characteristic of human serum, led to 30-40% inhibition of LDL oxidation in bicarbonate/CO2 buffer. Iron-catalyzed oxidation of LDL to MDA in phosphate buffer was inhibited by increasing concentrations of albumin (10-200 μM), whereas MDA formation in bicarbonate/CO2 buffer was stimulated by 10-50 μM albumin but inhibited by higher concentrations. However, albumin stimulated the oxidation of LDL proteins to carbonyl derivatives at all concentrations examined in both buffers. Conversion of LDL to MDA in bicarbonate/CO2 buffer was greatly stimulated by ADP, ATP, and EDTA but only when EDTA was added at a concentration equal to that of iron. At higher than stoichiometric concentrations, EDTA prevented oxidation of LDL. Results of these studies suggest that interactions between bicarbonate and iron or heme derivatives leads to complexes with redox potentials that favor the generation of reactive oxygen species and/or to the generation of highly reactive CO2 anion or bicarbonate radical that facilitates LDL oxidation. Freely available online through the PNAS open access option.Abbreviations: LDL, low-density lipoprotein; MDA, malondialdehyde; MetO, methionine sulfoxide.

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2012 CFR

2012-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2013 CFR

2013-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2014 CFR

2014-04-01

... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Foods § 73.200 Synthetic iron oxide. (a) Identity. (1) The... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

21 CFR 73.3125 - Iron oxides.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Iron oxides. 73.3125 Section 73.3125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR.... The color additive iron oxides (CAS Reg. No. 1332-37-2), Color Index No. 77491, shall conform in...

Preparation and characterization of iron oxide magnetic nanoparticles functionalized by nisin.

PubMed

Gruskiene, Ruta; Krivorotova, Tatjana; Staneviciene, Ramune; Ratautas, Dalius; Serviene, Elena; Sereikaite, Jolanta

2018-05-08

Nisin is a known bacteriocin approved as a food additive for food preservation. It exhibits a wide spectrum antimicrobial activity against Gram-positive bacteria. Iron oxide magnetic nanoparticles were synthesized and characterized by X-ray diffraction method. A main part of iron oxide nanoparticles was found to be maghemite though a small quantity of magnetite could also be present. Magnetic nanoparticles were stabilized by citric, ascorbic, gallic or glucuronic acid coating. Stable iron oxide magnetic nanoparticles were functionalized by nisin using a simple and low cost adsorption method. Nisin loading was confirmed by FT-IR spectra, thermogravimetric analysis, dynamic light scattering and atomic force microscopy methods. Nisin-loaded iron oxide magnetic nanoparticles were stable at least six weeks as judged by the measurements of zeta-potential and hydrodynamic diameter. The antimicrobial activity of nisin-loaded iron oxide magnetic nanoparticles was demonstrated toward Gram-positive bacteria. Functionalized nanoparticles could therefore find the application as antimicrobials in innovative and emerging technologies based on the magnetic field. Copyright © 2018 Elsevier B.V. All rights reserved.

An image processing approach for investigation on transport of iron oxide nanoparticles (FE3O4) stabilized with poly acrylic acid in two-dimensional porous media

NASA Astrophysics Data System (ADS)

Golzar, M.; Azhdary Moghaddam, M.; Saghravani, S. F.; Dahrazma, B.

2018-04-01

Iron oxide nanoparticles were stabilized using poly acrylic acid (PAA) to yield stabilized slurry of Iron oxide nanoparticles. A two-dimensional physical model filled by glass beads was used to study the fate and transport of the iron oxide nanoparticles stabilized with PAA in porous media under saturated, steady-state flow conditions. Transport data for a nonreactive tracer, slurry of iron oxide nanoparticles stabilized with PAA were collected under similar flow conditions. The results show that low concentration slurry of iron oxide nanoparticles stabilized with PAA can be transported like a tracer without significant retardation. The image processing technique was employed to measure the tracer/nanoparticle concentration inside the 2-D model filled with glass beads. The groundwater flow model, Visual MODFLOW, was used to model the observed transport patterns through MT3DMS module. Finally, it was demonstrated that the numerical model MODFLOW can be used to predict the fate and transport characteristics of nanoparticles stabilized with PAA in groundwater aquifers.

Effect of Organic Substances on the Efficiency of Fe(Ii) to Fe(Iii) Oxidation and Removal of Iron Compounds from Groundwater in the Sedimentation Process

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-09-01

One of the problems with iron removal from groundwater is organic matter. The article presents the experiments involved groundwater samples with a high concentration of total iron - amounting to 7.20 mgFe/dm3 and an increased amount of organic substances (TOC from 5.50 to 7.50 mgC/dm3). The water samples examined differed in terms of the value of the ratio of the TOC concentration and the concentration of total iron (D). It was concluded that with increase in the coexistence ratio of organic substances and total iron in water (D = [TOC]/[Fetot]), efficiency of Fe(II) to Fe(III) oxidization with dissolved oxygen decreased, while the oxidation time was increasing. This rule was not demonstrated for potassium manganate (VII) when used as an oxidizing agent. The application of potassium manganate (VII) for oxidation of Fe(II) ions produced the better results in terms of total iron concentration reduction in the sedimentation process than the oxidation with dissolved oxygen.

Ultrastructural study of iron oxide precipitates: implications for the search for biosignatures in the Meridiani hematite concretions, Mars.

PubMed

Souza-Egipsy, Virginia; Ormö, Jens; Beitler Bowen, Brenda; Chan, Marjorie A; Komatsu, Goro

2006-08-01

Two terrestrial environments that have been proposed as analogs for the iron oxide precipitation in the Meridiani Planum region of Mars include the Rio Tinto precipitates and southern Utah marble concretions. Samples of two typical Utah iron oxide concretions and iron oxide precipitates in contact with biofilms from Rio Tinto have been studied to determine whether evidence could be found for biomediation in the precipitation process and to identify likely locations for fossil microorganisms. Scanning electron microscopy, energy dispersive X-ray, and gas chromatography-mass spectrometry (GC-MS) were used to search for biosignatures in the Utah marbles. The precipitation of iron oxides resembles known biosignatures, though organic compounds could not be confirmed with GC-MS analysis. In contrast, textural variations induced by biological activity are abundant in the modern Rio Tinto samples. Although no compelling evidence of direct or indirect biomediation was found in the Utah marbles, the ultrastructure of the iron oxide cement in the concretion suggests an inward growth during concretion precipitation from an initially spherical redox front. No indication for growth from a physical nucleus was found.

Microbial Communities Associated with Biogenic Iron Oxide Mineralization in Circumneutral pH Environments

NASA Astrophysics Data System (ADS)

Chan, C. S.; Banfield, J. F.

2002-12-01

Lithotrophic growth on iron is a metabolism that has been found in a variety of neutral pH environments and is likely important in sustaining life in microaerophilic solutions, especially those low in organics. The composition of the microbial communities, especially the organisms that are responsible for iron oxidation, and carbon and nitrogen fixation, are not known, yet the ability to recognize these contributions is vital to our understanding of iron cycling in natural environments. Our approach has been to study the microbial community structure, mineralogy, and geochemistry of ~20 cm thick, 100's meters long, fluffy iron oxide-encrusted biological mats growing in the Piquette Mine tunnel, and to compare the results to those from geochemically similar environments. In situ measurements (Hydrolab) and geochemical characterization of bulk water samples and peepers (dialysis sampling vials) indicate that the environment is microaerobic, with micromolar levels of iron, high carbonate and sulfate, and typical groundwater nitrate and nitrite concentrations. 16S rDNA clone libraries show that the microbial mat and water contain communities with considerable diversity within the Bacterial domain, a large proportion of Nitrospira and Betaproteobacteria, and no Archaea. Because clone library data are not necessarily indicative of actual abundance, fluorescence in-situ hybridization (FISH) was performed on water, mat, and sediment samples from the Piquette mine and two circumneutral iron- and carbonate-rich springs in the Oregon Cascade Range. Domain- and phylum-level probes were chosen based on the clone library results (Nitrospira, Beta- and Gammaproteobacteria, Acidobacteria, Actinobacteria, Chloroflexi, and Planctomyces). FISH data reveal spatial associations between specific microbial groups and mineralized structures. The organisms responsible for making the mineralized sheaths that compose the bulk of the iron oxide mat are Betaproteobacteria (probably Leptothrix spp.). However, only a small proportion of the cells in the mat reside within the sheaths. Most are located on or around the sheaths, which provide a physical framework for the community. Preliminary results from FISH experiments on the iron-rich spring samples show some similarities, including an abundance of Betaproteobacteria. Enrichment and isolation experiments are being performed to identify the iron-oxidizing organisms. Iron-oxidizers have been enriched from all sites. In some cultures it has been difficult to isolate the iron-oxidizing organisms from a non-iron-oxidizing heterotroph, possibly indicating co-dependence. Knowledge of the microbial community structure and the metabolic activities of key members will enable us to better understand the processes and chemical conditions which generate iron oxide deposits found in the geologic record on Earth and possibly extraterrestrial habitats.

Controlled synthesis of magnetic iron oxides@SnO2 quasi-hollow core-shell heterostructures: formation mechanism, and enhanced photocatalytic activity.

PubMed

Wu, Wei; Zhang, Shaofeng; Ren, Feng; Xiao, Xiangheng; Zhou, Juan; Jiang, Changzhong

2011-11-01

Iron oxide/SnO(2) magnetic semiconductor core-shell heterostructures with high purity were synthesized by a low-cost, surfactant-free and environmentally friendly hydrothermal strategy via a seed-mediated method. The morphology and structure of the hybrid nanostructures were characterized by means of high-resolution transmission electron microscopy and X-ray diffraction. The morphology evolution investigations reveal that the Kirkendall effect directs the diffusion and causes the formation of iron oxide/SnO(2) quasi-hollow particles. Significantly, the as-obtained iron oxides/SnO(2) core-shell heterostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to as-used α-Fe(2)O(3) seeds and commercial SnO(2) products, mainly owing to the effective electron hole separation at the iron oxides/SnO(2) interfaces.

Protein Association and Dissociation Regulated by Ferric Ion

PubMed Central

Li, Chaorui; Fu, Xiaoping; Qi, Xin; Hu, Xiaosong; Chasteen, N. Dennis; Zhao, Guanghua

2009-01-01

Iron stored in phytoferritin plays an important role in the germination and early growth of seedlings. The protein is located in the amyloplast where it stores large amounts of iron as a hydrated ferric oxide mineral core within its shell-like structure. The present work was undertaken to study alternate mechanisms of core formation in pea seed ferritin (PSF). The data reveal a new mechanism for mineral core formation in PSF involving the binding and oxidation of iron at the extension peptide (EP) located on the outer surface of the protein shell. This binding induces aggregation of the protein into large assemblies of ∼400 monomers. The bound iron is gradually translocated to the mineral core during which time the protein dissociates back into its monomeric state. Either the oxidative addition of Fe2+ to the apoprotein to form Fe3+ or the direct addition of Fe3+ to apoPSF causes protein aggregation once the binding capacity of the 24 ferroxidase centers (48 Fe3+/shell) is exceeded. When the EP is enzymatically deleted from PSF, aggregation is not observed, and the rate of iron oxidation is significantly reduced, demonstrating that the EP is a critical structural component for iron binding, oxidation, and protein aggregation. These data point to a functional role for the extension peptide as an iron binding and ferroxidase center that contributes to mineralization of the iron core. As the iron core grows larger, the new pathway becomes less important, and Fe2+ oxidation and deposition occurs directly on the surface of the iron core. PMID:19398557

Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

NASA Astrophysics Data System (ADS)

van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

2014-05-01

Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone, with Fe(II) oxidation taking place in the soil surrounding the ditch during summer and in the surface water during winter. The dynamics in Fe(II) oxidation did not affect the dissolved P concentrations. The dissolved P concentrations of the in-stream reservoirs water were an order of magnitude lower than observed in the groundwater and have no seasonal trend. Our data showed preferential binding of P during initial stage of the Fe(II) oxidation process, indicating the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at the groundwater-surface water interface is an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and therefore a major control on the P retention in natural waters that drain anaerobic aquifers.

Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition

NASA Astrophysics Data System (ADS)

Hufschmid, Ryan; Arami, Hamed; Ferguson, R. Matthew; Gonzales, Marcela; Teeman, Eric; Brush, Lucien N.; Browning, Nigel D.; Krishnan, Kannan M.

2015-06-01

Superparamagnetic iron oxide nanoparticles (SPIONs) are used for a wide range of biomedical applications requiring precise control over their physical and magnetic properties, which are dependent on their size and crystallographic phase. Here we present a comprehensive template for the design and synthesis of iron oxide nanoparticles with control over size, size distribution, phase, and resulting magnetic properties. We investigate critical parameters for synthesis of monodisperse SPIONs by organic thermal decomposition. Three different, commonly used, iron containing precursors (iron oleate, iron pentacarbonyl, and iron oxyhydroxide) are evaluated under a variety of synthetic conditions. We compare the suitability of these three kinetically controlled synthesis protocols, which have in common the use of iron oleate as a starting precursor or reaction intermediate, for producing nanoparticles with specific size and magnetic properties. Monodisperse particles were produced over a tunable range of sizes from approximately 2-30 nm. Reaction parameters such as precursor concentration, addition of surfactant, temperature, ramp rate, and time were adjusted to kinetically control size and size-distribution, phase, and magnetic properties. In particular, large quantities of excess surfactant (up to 25 : 1 molar ratio) alter reaction kinetics and result in larger particles with uniform size; however, there is often a trade-off between large particles and a narrow size distribution. Iron oxide phase, in addition to nanoparticle size and shape, is critical for establishing magnetic properties such as differential susceptibility (dm/dH) and anisotropy. As an example, we show the importance of obtaining the required size and iron oxide phase for application to Magnetic Particle Imaging (MPI), and describe how phase purity can be controlled. These results provide much of the information necessary to determine which iron oxide synthesis protocol is best suited to a particular application.

Does a higher metal oxidation state necessarily imply higher reactivity toward H-atom transfer? A computational study of C-H bond oxidation by high-valent iron-oxo and -nitrido complexes.

PubMed

Geng, Caiyun; Ye, Shengfa; Neese, Frank

2014-04-28

In this work, the reactions of C-H bond activation by two series of iron-oxo ( (Fe(IV)), (Fe(V)), (Fe(VI))) and -nitrido model complexes ( (Fe(IV)), (Fe(V)), (Fe(VI))) with a nearly identical coordination geometry but varying iron oxidation states ranging from iv to vi were comprehensively investigated using density functional theory. We found that in a distorted octahedral coordination environment, the iron-oxo species and their isoelectronic nitrido analogues feature totally different intrinsic reactivities toward C-H bond cleavage. In the case of the iron-oxo complexes, the reaction barrier monotonically decreases as the iron oxidation state increases, consistent with the gradually enhanced electrophilicity across the series. The iron-nitrido complex is less reactive than its isoelectronic iron-oxo species, and more interestingly, a counterintuitive reactivity pattern was observed, i.e. the activation barriers essentially remain constant independent of the iron oxidation states. The detailed analysis using the Polanyi principle demonstrates that the different reactivities between these two series originate from the distinct thermodynamic driving forces, more specifically, the bond dissociation energies (BDEE-Hs, E = O, N) of the nascent E-H bonds in the FeE-H products. Further decomposition of the BDEE-Hs into the electron and proton affinity components shed light on how the oxidation states modulate the BDEE-Hs of the two series.

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

PubMed

Thomas, Daniel A; Coggon, Matthew M; Lignell, Hanna; Schilling, Katherine A; Zhang, Xuan; Schwantes, Rebecca H; Flagan, Richard C; Seinfeld, John H; Beauchamp, J L

2016-11-15

The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown. This study utilizes glycolaldehyde as a model organic species to examine the oxidation pathways and evolution of organic aerosol initiated by the photodissociation of aqueous iron(III) oxalate complexes. Hanging droplets (radius 1 mm) containing iron(III), oxalic acid, glycolaldehyde, and ammonium sulfate (pH ∼3) are exposed to irradiation at 365 nm and sampled at discrete time points utilizing field-induced droplet ionization mass spectrometry (FIDI-MS). Glycolaldehyde is found to undergo rapid oxidation to form glyoxal, glycolic acid, and glyoxylic acid, but the formation of high molecular weight oligomers is not observed. For comparison, particle-phase experiments conducted in a laboratory chamber explore the reactive uptake of gas-phase glycolaldehyde onto aqueous seed aerosol containing iron and oxalic acid. The presence of iron oxalate in seed aerosol is found to inhibit aerosol growth. These results suggest that photodissociation of iron(III) oxalate can lead to the formation of volatile oxidation products in tropospheric aqueous aerosols.

The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans.

PubMed

Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

2017-01-01

The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans , grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans , it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans , the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the -35 (or -24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

Iron(II) Initiation of Lipid and Protein Oxidation in Pork: The Role of Oxymyoglobin.

PubMed

Zhou, Feibai; Jongberg, Sisse; Zhao, Mouming; Sun, Weizheng; Skibsted, Leif H

2016-06-08

Iron(II), added as FeSO4·7H2O, was found to increase the rate of oxygen depletion as detected electrochemically in a pork homogenate from Longissimus dorsi through an initial increase in metmyoglobin formation from oxymyoglobin and followed by formation of primary and secondary lipid oxidation products and protein oxidation as detected as thiol depletion in myofibrillar proteins. Without added iron(II), under the same conditions at 37 °C, oxygen consumption corresponded solely to the slow oxymyoglobin autoxidation. Long-lived myofibrillar protein radicals as detected by ESR spectroscopy in the presence of iron(II) were formed subsequently to oxymyoglobin oxidation, and their level was increased by lipid oxidation when oxygen was completely depleted. Similarly, the time profile for formation of lipid peroxide indicated that oxymyoglobin oxidation initiates both protein oxidation and lipid oxidation.

Thermogravimetric analysis of the interaction of ferromagnetic metal atom and multiwalled carbon nanotubes.

PubMed

Rawat, Naveen; Gudyaka, Russel; Kumar, Mohit; Joshi, Bharat; Santhanam, Kalathur S V

2008-04-01

This paper describes the thermal oxidative behavior of atomized iron or atomized cobalt in the presence of multiwalled carbon nanotubes (MWCNT). The thermogravimetric analysis shows the atomized iron thermal oxidation starts at about 500 degrees C that is absent when the atomized iron is sintered with multiwalled carbon naonotubes. The thermal oxidation of iron in the sintered samples requires the collapse of the multiwalled carbon nanotubes. A similar behavior is observed with atomized cobalt when its oxidation requires the collapse of the nanotubes. This thermal oxidative shift is interpreted as due to the atomized iron or atomized cobalt atom experiencing extensive overlap and confinement effect with multiwalled carbon nanotubes causing a spin transfer. This confinement effect is suggested to produce a transformation of iron from the outermost electronic distribution of 3d64s2 to an effective configuration of 3d84s0 and for cobalt 3d74s2 to 3d94s0 producing spintronics effect.

Comparing highly ordered monolayers of nanoparticles fabricated using electrophoretic deposition: Cobalt ferrite nanoparticles versus iron oxide nanoparticles

DOE PAGES

Dickerson, James H.; Krejci, Alex J.; Garcia, Adriana -Mendoza; ...

2015-08-01

Ordered assemblies of nanoparticles remain challenging to fabricate, yet could open the door to many potential applications of nanomaterials. Here, we demonstrate that locally ordered arrays of nanoparticles, using electrophoretic deposition, can be extended to produce long-range order among the constituents. Voronoi tessellations along with multiple statistical analyses show dramatic increases in order compared with previously reported assemblies formed through electric field-assisted assembly. As a result, based on subsequent physical measurements of the nanoparticles and the deposition system, the underlying mechanisms that generate increased order are inferred.

Evaluation of Fe-containing Li2CuO2 on CO2 capture performed at different physicochemical conditions.

PubMed

Yañez-Aulestia, Ana; Ovalle-Encinia, Oscar; Pfeiffer, Heriberto

2018-06-05

Li 2 CuO 2 and different iron-containing Li 2 CuO 2 samples were synthesized by solid state reaction. On iron-containing samples, atomic sites of copper are substituted by iron ions in the lattice (XRD and Rietveld analyses). Iron addition induces copper release from Li 2 CuO 2 , which produce cationic vacancies and CuO, due to copper (Cu 2+ ) and iron (Fe 3+ ) valence differences. Two different physicochemical conditions were used for analyzing CO 2 capture on these samples; (i) high temperature and (ii) low temperature in presence of water vapor. At high temperatures, iron addition increased CO 2 chemisorption, due to structural and chemical variations on Li 2 CuO 2 . Kinetic analysis performed by first order reaction and Eyring models evidenced that iron addition on Li 2 CuO 2 induced a faster CO 2 chemisorption but a higher thermal dependence. Conversely, CO 2 chemisorption at low temperature in water vapor presence practically did not vary by iron addition, although hydration and hydroxylation processes were enhanced. Moreover, under these physicochemical conditions the whole sorption process became slower on iron-containing samples, due to metal oxides presence.

Multicopper oxidase-1 is a ferroxidase essential for iron homeostasis in Drosophila melanogaster

PubMed Central

Lang, Minglin; Braun, Caroline L.; Kanost, Michael R.; Gorman, Maureen J.

2012-01-01

Multicopper ferroxidases catalyze the oxidation of ferrous iron to ferric iron. In yeast and algae, they participate in cellular uptake of iron; in mammals, they facilitate cellular efflux. The mechanisms of iron metabolism in insects are still poorly understood, and insect multicopper ferroxidases have not been identified. In this paper, we present evidence that Drosophila melanogaster multicopper oxidase-1 (MCO1) is a functional ferroxidase. We identified candidate iron-binding residues in the MCO1 sequence and found that purified recombinant MCO1 oxidizes ferrous iron. An association between MCO1 function and iron homeostasis was confirmed by two observations: RNAi-mediated knockdown of MCO1 resulted in decreased iron accumulation in midguts and whole insects, and weak knockdown increased the longevity of flies fed a toxic concentration of iron. Strong knockdown of MCO1 resulted in pupal lethality, indicating that MCO1 is an essential gene. Immunohistochemistry experiments demonstrated that MCO1 is located on the basal surfaces of the digestive system and Malpighian tubules. We propose that MCO1 oxidizes ferrous iron in the hemolymph and that the resulting ferric iron is bound by transferrin or melanotransferrin, leading to iron storage, iron withholding from pathogens, regulation of oxidative stress, and/or epithelial maturation. These proposed functions are distinct from those of other known ferroxidases. Given that MCO1 orthologues are present in all insect genomes analyzed to date, this discovery is an important step toward understanding iron metabolism in insects. PMID:22847425

Microanalysis of iron oxidation state in iron oxides using X Ray Absorption Near Edge Structure (XANES)

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Delaney, J.; Bajt, S.; Rivers, M. L.; Smith, J. V.

1993-01-01

An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.

Unravelling the cross-talk between iron starvation and oxidative stress responses highlights the key role of PerR (alr0957) in peroxide signalling in the cyanobacterium Nostoc PCC 7120.

PubMed

Yingping, Fan; Lemeille, Sylvain; Talla, Emmanuel; Janicki, Annick; Denis, Yann; Zhang, Cheng-Cai; Latifi, Amel

2014-10-01

The cyanobacterial phylum includes oxygenic photosynthetic prokaryotes of a wide variety of morphologies, metabolisms and ecologies. Their adaptation to their various ecological niches is mainly achieved by sophisticated regulatory mechanisms and depends on a fine cross-talk between them. We assessed the global transcriptomic response of the filamentous cyanobacterium Nostoc PCC 7120 to iron starvation and oxidative stress. More than 20% of the differentially expressed genes in response to iron stress were also responsive to oxidative stress. These transcripts include antioxidant proteins-encoding genes that confirms that iron depletion leads to reactive oxygen accumulation. The activity of the Fe-superoxide dismutase was not significantly decreased under iron starvation, indicating that the oxidative stress generated under iron deficiency is not a consequence of (SOD) deficiency. The transcriptional data indicate that the adaptation of Nostoc to iron-depleted conditions displays important differences with what has been shown in unicellular cyanobacteria. While the FurA protein that regulates the response to iron deprivation has been well characterized in Nostoc, the regulators in charge of the oxidative stress response are unknown. Our study indicates that the alr0957 (perR) gene encodes the master regulator of the peroxide stress. PerR is a peroxide-sensor repressor that senses peroxide by metal-catalysed oxidation.

Iron cycling at corroding carbon steel surfaces.

PubMed

Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.

Iron cycling at corroding carbon steel surfaces

PubMed Central

Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

Fluoride-induced iron overload contributes to hepatic oxidative damage in mouse and the protective role of Grape seed proanthocyanidin extract.

PubMed

Niu, Qiang; He, Ping; Xu, Shangzhi; Ma, Ruling; Ding, Yusong; Mu, Lati; Li, Shugang

2018-01-01

Emerging evidence has demonstrated that iron overload plays an important role in oxidative stress in the liver. This study aimed to explore whether fluoride-induced hepatic oxidative stress is associated with iron overload and whether grape seed proanthocyanidin extract (GSPE) alleviates oxidative stress by reducing iron overload. Forty Kunming male mice were randomly divided into 4 groups and treated for 5 weeks with distilled water (control), sodium fluoride (NaF) (100 mg/L), GSPE (400 mg/kg bw), or NaF (100 mg/L) + GSPE (400 mg/kg bw). Mice exposed to NaF showed typical poisoning changes of morphology, increased aspartate aminotransferase and alanine aminotransferase activities in the liver. NaF treatment also increased MDA accumulation, decreased GSH-Px, SOD and T-AOC levels in liver, indicative of oxidative stress. Intriguingly, all these detrimental effects were alleviated by GSPE. Further study revealed that NaF induced disorders of iron metabolism, as manifested by elevated iron level with increased hepcidin but decreased ferroportin expression, which contributed to hepatic oxidative stress. Importantly, the iron dysregulation induced by NaF could be normalized by GSPE. Collectively, these data provide a novel insight into mechanisms underlying fluorosis and highlight the potential of GSPE as a naturally occurring prophylactic treatment for fluoride-induced hepatotoxicity associated with iron overload.

Microbial Iron Cycling in Acidic Geothermal Springs of Yellowstone National Park: Integrating Molecular Surveys, Geochemical Processes, and Isolation of Novel Fe-Active Microorganisms

PubMed Central

Kozubal, Mark A.; Macur, Richard E.; Jay, Zackary J.; Beam, Jacob P.; Malfatti, Stephanie A.; Tringe, Susannah G.; Kocar, Benjamin D.; Borch, Thomas; Inskeep, William P.

2012-01-01

Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 88°C and pH 2.4 to 3.6. All iron oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65–70°C, but increased in diversity below 60°C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were measured for M. yellowstonensis str. MK1 and Sulfolobales str. MK5. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88°C. PMID:22470372

The Effect of Citric Acid on the Oxidation of Organic Contaminants by Fenton's Reagent

NASA Astrophysics Data System (ADS)

Seol, Y.; Javandel, I.; Lee, G.

2003-12-01

Combined with acids and iron catalysts, hydrogen peroxide (H2O2) as Fenton's reagent is proven to be effective in oxidizing halogenated volatile organic compounds (VOCs). The Fenton's reagent, traditionally used for waste water treatment technique, has been applied to the remediation of contaminated soil systems and numerous investigators have found intrinsic iron salts are effective source of iron catalyst for the reaction. Citric acid, which is naturally occurring nutrients to microorganisms and less destructive to soil chemical properties, is selected for an acidifying agent to create acidic soil condition. However, citric acid has been considered as a reaction inhibitant because it sequesters ferric iron from Fenton's catalytic cycle by forming strong chelates with iron. This paper presents the feasibility of using citric acid as an acidifying agent of soil matrix for the Fenton-like oxidation. Series of batch tests were performed to test disappearance of VOCs in various aqueous systems with two acidifying agents (citric acid or sulfuric acid) and three iron sources (iron sulfate, water soluble soil iron, or soil matrix). Batch results show that soluble iron is essential for near complete disappearance of VOCs and that citric acid performs similarly to sulfuric acid at low H2O2 dosage (< 1 wt%). The test soil provided water-soluble soil iron but also contained scavengers of the oxidizing agents, resulting in limited removals of VOCs. Column tests confirmed the results of the batch tests, suggesting citric acid is also as effective as sulfuric acid in providing acidic environment for the Fenton-like oxidation. The batch experiments also reveal that higher doses of H2O2 lower the degree of VOC removals in citric acid systems. Potential explanations for this declining include that excessive presence of H2O2 expedites the oxidation of ferrous to ferric iron, which then forms a strong complex with citrate, leading to the sequestration of the iron from the Fenton's reaction cycle. Consequently, additional supply of ferrous iron would be required for continuing oxidation of VOCs, as well as slow injection of H2O2. Detailed mechanistic study would be needed for factual understanding.

Additional oxidative stress reroutes the global response of Aspergillus fumigatus to iron depletion.

PubMed

Kurucz, Vivien; Krüger, Thomas; Antal, Károly; Dietl, Anna-Maria; Haas, Hubertus; Pócsi, István; Kniemeyer, Olaf; Emri, Tamás

2018-05-10

Aspergillus fumigatus has to cope with a combination of several stress types while colonizing the human body. A functional interplay between these different stress responses can increase the chances of survival for this opportunistic human pathogen during the invasion of its host. In this study, we shed light on how the H 2 O 2 -induced oxidative stress response depends on the iron available to this filamentous fungus, using transcriptomic analysis, proteomic profiles, and growth assays. The applied H 2 O 2 treatment, which induced only a negligible stress response in iron-replete cultures, deleteriously affected the fungus under iron deprivation. The majority of stress-induced changes in gene and protein expression was not predictable from data coming from individual stress exposure and was only characteristic for the combination of oxidative stress plus iron deprivation. Our experimental data suggest that the physiological effects of combined stresses and the survival of the fungus highly depend on fragile balances between economization of iron and production of essential iron-containing proteins. One observed strategy was the overproduction of iron-independent antioxidant proteins to combat oxidative stress during iron deprivation, e.g. the upregulation of superoxide dismutase Sod1, the thioredoxin reductase Trr1, and the thioredoxin orthologue Afu5g11320. On the other hand, oxidative stress induction overruled iron deprivation-mediated repression of several genes. In agreement with the gene expression data, growth studies underlined that in A. fumigatus iron deprivation aggravates oxidative stress susceptibility. Our data demonstrate that studying stress responses under separate single stress conditions is not sufficient to understand how A. fumigatus adapts in a complex and hostile habitat like the human body. The combinatorial stress of iron depletion and hydrogen peroxide caused clear non-additive effects upon the stress response of A. fumigatus. Our data further supported the view that the ability of A. fumigatus to cause diseases in humans strongly depends on its fitness attributes and less on specific virulence factors. In summary, A. fumigatus is able to mount and coordinate complex and efficient responses to combined stresses like iron deprivation plus H 2 O 2 -induced oxidative stress, which are exploited by immune cells to kill fungal pathogens.

Iron supplementation at high altitudes induces inflammation and oxidative injury to lung tissues in rats

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

Salama, Samir A., E-mail: salama.3@buckeyemail.osu.edu; Department of Biochemistry, Faculty of Pharmacy, Al-Azhar University, Cairo 11751; Department of Pharmacology and GTMR Unit, College of Clinical Pharmacy, Taif University, Al-Haweiah, Taif 21974

2014-01-01

Exposure to high altitudes is associated with hypoxia and increased vulnerability to oxidative stress. Polycythemia (increased number of circulating erythrocytes) develops to compensate the high altitude associated hypoxia. Iron supplementation is, thus, recommended to meet the demand for the physiological polycythemia. Iron is a major player in redox reactions and may exacerbate the high altitudes-associated oxidative stress. The aim of this study was to explore the potential iron-induced oxidative lung tissue injury in rats at high altitudes (6000 ft above the sea level). Iron supplementation (2 mg elemental iron/kg, once daily for 15 days) induced histopathological changes to lung tissuesmore » that include severe congestion, dilatation of the blood vessels, emphysema in the air alveoli, and peribronchial inflammatory cell infiltration. The levels of pro-inflammatory cytokines (IL-1β, IL-6, and TNF-α), lipid peroxidation product and protein carbonyl content in lung tissues were significantly elevated. Moreover, the levels of reduced glutathione and total antioxidant capacity were significantly reduced. Co-administration of trolox, a water soluble vitamin E analog (25 mg/kg, once daily for the last 7 days of iron supplementation), alleviated the lung histological impairments, significantly decreased the pro-inflammatory cytokines, and restored the oxidative stress markers. Together, our findings indicate that iron supplementation at high altitudes induces lung tissue injury in rats. This injury could be mediated through excessive production of reactive oxygen species and induction of inflammatory responses. The study highlights the tissue injury induced by iron supplementation at high altitudes and suggests the co-administration of antioxidants such as trolox as protective measures. - Highlights: • Iron supplementation at high altitudes induced lung histological changes in rats. • Iron induced oxidative stress in lung tissues of rats at high altitudes. • Iron increased the levels of IL-1β, IL-6 and TNF-α in lung tissues at high altitudes. • Trolox alleviated the iron-induced histological and biochemical changes to the lungs.« less

Process for the synthesis of iron powder

DOEpatents

Welbon, W.W.

1983-11-08

A process for preparing iron powder suitable for use in preparing the iron-potassium perchlorate heat-powder fuel mixture used in thermal batteries, comprises preparing a homogeneous, dense iron oxide hydroxide precipitate by homogeneous precipitation from an aqueous mixture of a ferric salt, formic or sulfuric acid, ammonium hydroxide and urea as precipitating agent; and then reducing the dense iron oxide hydroxide by treatment with hydrogen to prepare the iron powder. 2 figs.

Iron-mediated redox modulation in neural plasticity

PubMed Central

Muñoz, Pablo

2012-01-01

The role of iron in brain physiology has focused on the neuropathological, effects due to iron-induced oxidative stress. However, our recent work has established a physiological relationship between the iron-mediated oxidative modification and normal neuronal function. Our results obtained from hippocampal neurons, suggest that iron-generated reactive species oxygen (ROS) are involved in calcium signaling initiated by stimulation of NMDA receptors. This signal is amplified by ryanodine receptors (RyR), a redox- sensitive calcium channel, allowing the phosphorylation and nuclear translocation of ERK1/2. Furthermore, using electrophysiological approaches, we showed that iron is required for basal synaptic transmission and full expression of long-term potentiation, a type of synaptic plasticity. Our data combined suggest that the oxidative effect of iron is critical to activate processes that are downstream of NMDAR activation. Finally, due to the high reactivity of DNA with iron-generated ROS, we hypothesize an additional function of iron in gene regulation. PMID:22808323

Removal of iron and manganese using biological roughing up flow filtration technology.

PubMed

Pacini, Virginia Alejandra; María Ingallinella, Ana; Sanguinetti, Graciela

2005-11-01

The removal of iron and manganese from groundwater using biological treatment methods is almost unknown in Latin America. Biological systems used in Europe are based on the process of double rapid biofiltration during which dissolved oxygen and pH need to be strictly controlled in order to limit abiotic iron oxidation. The performance of roughing filter technology in a biological treatment process for the removal of iron and manganese, without the use of chemical agents and under natural pH conditions was studied. Two pilot plants, using two different natural groundwaters, were operated with the following treatment line: aeration, up flow roughing filtration and final filtration (either slow or rapid). Iron and manganese removal efficiencies were found to be between 85% and 95%. The high solid retention capability of the roughing filter means that it is possible to remove iron and manganese simultaneously by biotic and abiotic mechanisms. This system combines simple, low-cost operation and maintenance with high iron and manganese removal efficiencies, thus constituting a technology which is particularly suited to small waterworks.

Reductive dechlorination of trichloroethylene by iron bimetallics

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

Orth, R.G.; Dauda, T.; McKenzie, D.E.

1998-07-01

Reductive dechlorination using a zero valence metal such as iron has seen an increase in interest with the extension of iron dechlorination to in-situ treatment of ground water. Studies to increase the rate of dechlorination and the long term stability have lead many to examine the use of bimetallic iron systems. Results are shown for bimetallic iron systems of Cu, Sn, Ni, Ag, Au, and Pd. All of these bimetallic couples form a galvanic couple which increase corrosion rates and the production of hydrogen. Increased rates of reaction normalized to surface area were observed for all the couples. The reactionmore » rates were found to depended on surface area and surface coverage of the iron. The results of studies in deuterium oxide indicate that the pathways changed as the bimetallic is changed and that the pathway in all cases could be a combination of dehydrohalgenation and sequential dechlorination. Degradation of DNAPL TCE by iron was found to be zero order and the type of product observed was different from that observed for TCE dissolved in water.« less

One-step synthesis of magnetic chitosan polymer composite films

NASA Astrophysics Data System (ADS)

Cesano, Federico; Fenoglio, Gaia; Carlos, Luciano; Nisticò, Roberto

2015-08-01

In this study, a magnetic iron oxide-chitosan composite film is synthesized by one-step method and thoroughly investigated in order to better understand its inorganic/organic properties. A deep physico-chemical characterization of the magnetic films has been performed. In particular, the material composition was evaluated by means of XRD and ATR-FTIR spectroscopy, whereas the thermal stability and the subsequent inorganic phase transitions involving iron oxide species were followed by TGA analyses carried out at different experimental conditions (i.e. inert and oxidative atmosphere). The magnetic properties of the films were tested at the bulk and at the surface level, performing respectively magnetization hysteresis curve and magnetic force microscopy (MFM) surface mapping. Results indicate that the synthesized material can be prepared through a very simple synthetic procedure and suggests that it can be successfully applied for instance to environmental applications, such as the adsorption of contaminants from solid and liquid media thanks to its pronounced magnetic properties, which favour its recover.

Kinetic behavior of Fe(o,o-EDDHA)-humic substance mixtures in several soil components and in calcareous soils.

PubMed

Cerdán, Mar; Alcañiz, Sara; Juárez, Margarita; Jordá, Juana D; Bermúdez, Dolores

2007-10-31

Ferric ethylenediamine- N, N'-bis-(o-hydroxyphenylacetic)acid chelate (Fe(o, o-EDDHA)) is one of the most effective Fe fertilizers in calcareous soils. However, humic substances are occasionally combined with iron chelates in drip irrigation systems in order to lower costs. The reactivity of iron chelate-humic substance mixtures in several soil components and in calcareous soils was investigated through interaction tests, and their behavior was compared to the application of iron chelates and humic substances separately. Two commercial humic substances and two Fe(o, o-EDDHA) chelates (one synthesized in the laboratory and one commercial) were used to prepare iron chelate-humic substance mixtures at 50% (w/w). Various soil components (calcium carbonate, gibbsite, amorphous iron oxide, hematite, tenorite, zincite, amorphous Mn oxide, and peat) and three calcareous soils were shaken for 15 days with the mixtures and with iron chelate and humic substance solutions. The kinetic behavior of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) (Fe bonded to (o,p-EDDHA) and other polycondensated ligands) and of the different nutrients solubilized after the interaction assay was determined. The results showed that the mixtures did not significantly reduce the retention of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) in the soil components and the calcareous soils compared to the iron chelate solutions, but they did produce changes in the retention rate. Moreover, the competition between humic substances and synthetic chelating agents for complexing metal cations limited the effectiveness of the mixtures to mobilize nutrients from the substrates. The presence of Fe(o, p-EDDHA) and other byproducts in the commercial iron chelate had an important effect on the evolution of Fe(o, o-EDDHA) and the nutrient solubilization process.

Enhanced removal of ethanolamine from secondary system of nuclear power plant wastewater by novel hybrid nano zero-valent iron and pressurized ozone initiated oxidation process.

PubMed

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

2017-07-01

Monoethanolamine (shortly ethanolamine (ETA)), usually used as a corrosion inhibitor, is a contaminant of wastewater from the secondary cooling system of nuclear power plants (NPPs) and is not readily biodegradable. We conducted various experiments, including treatments with nano zero-valent iron (nZVI), nano-iron/calcium, and calcium oxide (nFe/Ca/CaO) with ozone (O 3 ) or hydrogen peroxide (H 2 O 2 ) to reduce the concentration of ETA and to decrease the chemical demand of oxygen (COD) of these wastewaters. During this study, wastewater with ETA concentration of 7465 mg L -1 and COD of 6920 mg L -1 was used. As a result, the ETA concentration was reduced to 5 mg L -1 (a decrease of almost 100%) and COD was reduced to 2260 mg L -1 , a reduction of 67%, using doses of 26.8 mM of nZVI and 1.5 mM of H 2 O 2 at pH 3 for 3 h. Further treatment for 48 h allowed a decrease of COD by almost 97%. Some mechanistic considerations are proposed in order to explain the degradation pathway. The developed hybrid nano zero-valent iron-initiated oxidation process with H 2 O 2 is promising in the treatment of ETA-contaminated wastewaters.

Characterization of Fe-leonardite complexes as novel natural iron fertilizers.

PubMed

Kovács, Krisztina; Czech, Viktória; Fodor, Ferenc; Solti, Adam; Lucena, Juan J; Santos-Rosell, Sheila; Hernández-Apaolaza, Lourdes

2013-12-18

Water-soluble humic substances (denoted by LN) extracted at alkaline pH from leonardite are proposed to be used as complexing agents to overcome micronutrient deficiencies in plants such as iron chlorosis. LN presents oxidized functional groups that can bind Fe(2+) and Fe(3+). The knowledge of the environment of Fe in the Fe-LN complexes is a key point in the studies on their efficacy as Fe fertilizers. The aim of this work was to study the Fe(2+)/Fe(3+) species formed in Fe-LN complexes with (57)Fe Mössbauer spectroscopy under different experimental conditions in relation to the Fe-complexing capacities, chemical characteristics, and efficiency to provide iron in hydroponics. A high oxidation rate of Fe(2+) to Fe(3+) was found when samples were prepared with Fe(2+), although no well-crystalline magnetically ordered ferric oxide formation could be observed in slightly acidic or neutral media. It seems to be the case that the formation of Fe(3+)-LN compounds is favored over Fe(2+)-LN compounds, although at acidic pH no complex formation between Fe(3+) and LN occurred. The Fe(2+)/Fe(3+) speciation provided by the Mössbauer data showed that Fe(2+)-LN could be efficient in hydroponics while Fe(3+)-LN is suggested to be used more effectively under calcareous soil conditions. However, according to the biological assay, Fe(3+)-LN proved to be effective as a chlorosis corrector applied to iron-deficient cucumber in nutrient solution.

Iron Oxide as an MRI Contrast Agent for Cell Tracking

PubMed Central

Korchinski, Daniel J.; Taha, May; Yang, Runze; Nathoo, Nabeela; Dunn, Jeff F.

2015-01-01

Iron oxide contrast agents have been combined with magnetic resonance imaging for cell tracking. In this review, we discuss coating properties and provide an overview of ex vivo and in vivo labeling of different cell types, including stem cells, red blood cells, and monocytes/macrophages. Furthermore, we provide examples of applications of cell tracking with iron contrast agents in stroke, multiple sclerosis, cancer, arteriovenous malformations, and aortic and cerebral aneurysms. Attempts at quantifying iron oxide concentrations and other vascular properties are examined. We advise on designing studies using iron contrast agents including methods for validation. PMID:26483609

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2011 CFR

2011-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

21 CFR 73.200 - Synthetic iron oxide.

Code of Federal Regulations, 2010 CFR

2010-04-01

... suitable and that are listed in this subpart as safe for use in color additive mixtures for coloring foods... food. (2) Synthetic iron oxide may be safely used for the coloring of dog and cat foods in an amount... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Synthetic iron oxide. 73.200 Section 73.200 Food...

The tortoise versus the hare - Possible advantages of microparticulate zerovalent iron (mZVI) over nanoparticulate zerovalent iron (nZVI) in aerobic degradation of contaminants.

PubMed

Ma, Jinxing; He, Di; Collins, Richard N; He, Chuanshu; Waite, T David

2016-11-15

A comparative study of the ability of microparticulate zerovalent iron (mZVI) and nanoparticulate zerovalent iron (nZVI) to oxidize a target compound (in this study, 14 C-labelled formate) under aerobic conditions has been conducted with specific consideration given to differences in reaction mechanisms. Results of Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy showed that mZVI underwent a slow transformation to ferrihydrite while nZVI, in contrast, rapidly transformed into lepidocrocite. The behavior of mZVI (compared to nZVI) could be attributed to either (i) a lower reactivity with oxygen and/or water, (ii) surface passivation by ferrihydrite resulting in reduced electron conductivity, and/or (iii) the relatively low concentration of Fe(II) which, in the case of nZVI, catalyzed the transformation of ferrihydrite to lepidocrocite. The influence of these structural transformations on contaminant removal was profound with the ferrihydrite that formed on mZVI inducing rapid adsorption of formate and moderating reactions of mZVI with oxygen and/or water. Although surface passivation of mZVI was significant, the effectiveness of the ensuing heterogeneous redox reactions in the mZVI/O 2 system, as characterized by the molar ratio of oxidized formate to consumed Fe(0) (i.e., 13.7 ± 0.8 μM/M), was comparable to that for nZVI (16.5 ± 1.4 μM/M). The results of this study highlight the potential of mZVI for the oxidative degradation of target organics in preference to nZVI despite its lower intrinsic reactivity though some means (either natural or engineered) of inducing continual depassivation of the iron oxyhydroxide-coated mZVI would be required in order to maintain ongoing oxidant production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

EPA Science Inventory

Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

Iron content of soils as a precipitation proxy

NASA Astrophysics Data System (ADS)

Dzombak, R.; Sheldon, N. D.

2016-12-01

Given that different iron phases form under different precipitation and drainage regimes, soil iron content could be used as a proxy for both volume and seasonality of precipitation. Constraining these factors is important for predicting future precipitation trends, especially for a warmer climate that will likely see more frequent extreme weather events. Specifically, using paleoprecipitation data from periods of higher temperatures and atmospheric CO2 concentrations helps inform models of future `greenhouse' climate. Forty-five modern samples from across the continental United States were analyzed, with MAP ranging from 200 to 1200 mm yr-1 and MAT ranging from 5 to 22°C. Soil types included Alfisols (N=15), Inceptisols (N=8), Mollisols (N=15), and Aridisols (N=7), and ranged from seasonally wet to well-drained. Analytical techniques included combustion-elemental analysis and organic carbon isotope analysis, a sequential iron extraction modified with a sodium hypochlorite step for the extraction of organic matter-bound iron, and the extraction of iron sulfides. The sequential extractions yield five different `pools' of iron found in sediment: crystalline iron oxides (e.g., goethite, hematite), magnetite, carbonate-bound, organic matter-bound, and labile/easily reducible iron minerals (e.g., ferrihydrite). Analysis by ICP-OES yielded a strong relationship between magnetite-bound iron and MAP, and fair relationships between the other iron pools and MAP. Individual soil orders tended to show stronger relationships to the iron pools than all soils analyzed together, potentially indicating the need for separate proxy relationships for each soil order. Pyrite concentrations were well below 1% by weight for these soils, suggesting that none of these soils has a long enough wet season to encourage its formation and that the presence vs. absence of pyrite in paleosols may be a useful proxy for soil moisture state. In contrast to some earlier work, no significant relationship was found between A horizon δ13C and MAP, but one may emerge as the size of the dataset increases. Ongoing work will include a wider selection of modern soils, increasing the range of both precipitation and temperature, the number of soil orders, and the degree of drainage.

Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents

NASA Astrophysics Data System (ADS)

Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B.; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

2014-07-01

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI. Electronic supplementary information (ESI) available: A detailed description of the synthesis of the ligands as well as the preparation and functionalization of the iron oxide nanoparticles including their physico-chemical characterization are presented. Further, details of the cell experiments and the SPR experiments are given. Two representative movies are provided showing leukocyte rolling on the ligand coated surface of the flow chamber. See DOI: 10.1039/c3nr04793h

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 crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.

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.

The effect of Mg dopants on magnetic and structural properties of iron oxide and zinc ferrite thin films

NASA Astrophysics Data System (ADS)

Saritaş, Sevda; Ceviz Sakar, Betul; Kundakci, Mutlu; Yildirim, Muhammet

2018-06-01

Iron oxide thin films have been obtained significant interest as a material that put forwards applications in photovoltaics, gas sensors, biosensors, optoelectronic and especially in spintronics. Iron oxide is one of the considerable interest due to its chemical and thermal stability. Metallic ion dopant influenced superexchange interactions and thus changed the structural, electrical and magnetic properties of the thin film. Mg dopped zinc ferrite (Mg:ZnxFe3-xO4) crystal was used to avoid the damage of Fe3O4 (magnetite) crystal instead of Zn2+ in this study. Because the radius of the Mg2+ ion in the A-site (tetrahedral) is almost equal to that of the replaced Fe3+ ion. Inverse-spinel structure in which oxygen ions (O2-) are arranged to form a face-centered cubic (FCC) lattice where there are two kinds of sublattices, namely, A-site and B-site (octahedral) interstitial sites and in which the super exchange interactions occur. In this study, to increase the saturation of magnetization (Ms) value for iron oxide, inverse-spinal ferrite materials have been prepared, in which the iron oxide was doped by multifarious divalent metallic elements including Zn and Mg. Triple and quaternary; iron oxide and zinc ferrite thin films with Mg metal dopants were grown by using Spray Pyrolysis (SP) technique. The structural, electrical and magnetic properties of Mg dopped iron oxide (Fe2O3) and zinc ferrite (ZnxFe3-xO4) thin films have been investigated. Vibrating Sample Magnetometer (VSM) technique was used to study for the magnetic properties. As a result, we can say that Mg dopped iron oxide thin film has huge diamagnetic and of Mg dopped zinc ferrite thin film has paramagnetic property at bigger magnetic field.

Novel electrochemical-enzymatic model which quantifies the effect of the solution Eh on the kinetics of ferrous iron oxidation with Acidithiobacillus ferrooxidans.

PubMed

Meruane, G; Salhe, C; Wiertz, J; Vargas, T

2002-11-05

The influence of solution Eh on the rate of ferrous iron oxidation by Acidithiobacillus ferrooxidans is characterized. The experimental approach was based on the use of a two-chamber bioelectrochemical cell, which can determine the ferrous iron oxidation rate at controlled potential. Results enabled the formulation of a novel kinetic model, which incorporates the effect of solution Eh in an explicit form but still integrates the effect of ferrous iron concentration and ferric inhibition. The results showed that at Eh values below 650 mV (standard hydrogen electrode, SHE) the bacterial oxidative activity is mainly dependent on ferrous iron concentration. At Eh values between 650 and 820 mV (SHE) the oxidation rate is mainly controlled by ferric inhibition. Over 820 mV (SHE) the bacterial oxidative activity is strongly inhibited by the Eh increase, being completely inhibited at Eh = 840 mV (SHE). Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 80: 280-288, 2002.

Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

USGS Publications Warehouse

McKnight, Diane M.; Bencala, K.E.

1989-01-01

A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream. ?? 1989.

Oxygen in the Martian atmosphere: Regulation of PO2 by the deposition of iron formations on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1992-01-01

During Earth's early history, and prior to the evolution of its present day oxygenated atmosphere, extensive iron rich siliceous sedimentary rocks were deposited, consisting of alternating layers of silica (chert) and iron oxide minerals (hematite and magnetite). The banding in iron formations recorded changes of atmosphere-hydrosphere interactions near sea level in the ancient ocean, which induced the oxidation of dissolved ferrous iron, precipitation of insoluble ferric oxides and silica, and regulation of oxygen in Earth's early atmosphere. Similarities between the Archean Earth and the composition of the present day atmosphere on Mars, together with the pervasive presence of ferric oxides in the Martian regolith suggest that iron formation might also have been deposited on Mars and influenced the oxygen content of the Martian atmosphere. Such a possibility is discussed here with a view to assessing whether the oxygen content of the Martian atmosphere has been regulated by the chemical precipitation of iron formations on Mars.

Design of Fucoidan Functionalized - Iron Oxide Nanoparticles for Biomedical Applications.

PubMed

Tran, Khanh Nghia; Tran, Phuong Ha-Lien; Vo, Toi Van; Tran, Thao Truong-Dinh

2016-01-01

This research aims to develop an iron oxide nanoparticle drug delivery system utilizing a recent material discovered from ocean, fucoidan. The material has drawn much interest due to many biomedical functions that have been proven for human health. One interesting point herein is that fucoidan is not only a sulfated polysaccharide, a polymer for stabilization of iron oxide nanoparticles, but plays a role of an anticancer agent also. Various approaches were investigated to optimize the high loading efficiency and explain the mechanism of nanoparticle formations. Fucoidan was functionalized on iron oxide nanoparticles by a direct coating or via amine groups. Also, a hydrophobic part of oleic acid was conjugated to the amine groups for a more favorable loading of poorly water-soluble anticancer drugs. This study proposed a novel system and an efficient method to functionalize fucoidan on iron oxide nanoparticle systems which will lead to a facilitation of a double strength treatment of cancer.

Interaction of aromatic amines with iron oxides: implications for prebiotic chemistry.

PubMed

Shanker, Uma; Singh, Gurinder; Kamaluddin

2013-06-01

The interaction of aromatic amines (aniline, p-chloroaniline, p-toludine and p-anisidine) with iron oxides (goethite, akaganeite and hematite) has been studied. Maximum uptake of amines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was found to be a better adsorbate probably due to its higher basicity. In alkaline medium (pH > 8), amines reacted on goethite and akaganeite to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer. IR analysis of the amine-iron oxide hydroxide adduct suggests that the surface acidity of iron oxide hydroxides is responsible for the interaction. The present study suggests that iron oxide hydroxides might have played a role in the stabilization of organic molecules through their surface activity and in prebiotic condensation reactions.

Evaluation of the Effects of Iron Oxides on Soil Reducing Conditions and Methane Generation in Cambodian Wetland Rice Fields

NASA Astrophysics Data System (ADS)

Weaver, M.; Benner, S.; Fendorf, S.; Sampson, M.; Leng, M.

2007-12-01

Atmospheric concentrations of methane have been steadily increasing over the last 100 years, which has given rise to research of wetland rice fields, recently identified as a major anthropomorphic source of methane. Establishment of experimental soil pots, cultivating an aromatic early variety rice strain in the Kean Svay District of Cambodia, have recently been carried out to evaluate methods to minimize methane release by promoting redox buffering by iron oxides. In the first series of experiments, iron oxides were added to the soils and the rate of change in reducing conditions and methanogenesis onset was monitored. In the second series of experiments, plots are subject to periodic drying cycles to promote rejuvenation of buffering iron oxides. Initial results indicate a delay in the onset of methanogenesis, and overall methane generation, in plots where initial iron oxides concentrations are elevated.

Soft template strategy to synthesize iron oxide-titania yolk-shell nanoparticles as high-performance anode materials for lithium-ion battery applications.

PubMed

Lim, Joohyun; Um, Ji Hyun; Ahn, Jihoon; Yu, Seung-Ho; Sung, Yung-Eun; Lee, Jin-Kyu

2015-05-18

Yolk-shell-structured nanoparticles with iron oxide core, void, and a titania shell configuration are prepared by a simple soft template method and used as the anode material for lithium ion batteries. The iron oxide-titania yolk-shell nanoparticles (IO@void@TNPs) exhibit a higher and more stable capacity than simply mixed nanoparticles of iron oxide and hollow titania because of the unique structure obtained by the perfect separation between iron oxide nanoparticles, in combination with the adequate internal void space provided by stable titania shells. Moreover, the structural effect of IO@void@TNPs clearly demonstrates that the capacity retention value after 50 cycles is approximately 4 times that for IONPs under harsh operating conditions, that is, when the temperature is increased to 80 °C. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of coating an iron-based article

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

Magdefrau, Neal; Beals, James T.; Sun, Ellen Y.

A method of coating an iron-based article includes a first heating step of heating a substrate that includes an iron-based material in the presence of an aluminum source material and halide diffusion activator. The heating is conducted in a substantially non-oxidizing environment, to cause the formation of an aluminum-rich layer in the iron-based material. In a second heating step, the substrate that has the aluminum-rich layer is heated in an oxidizing environment to oxidize the aluminum in the aluminum-rich layer.

Microwave-assisted combustion synthesis of nano iron oxide/iron-coated activated carbon, anthracite, cellulose fiber, and silica, with arsenic adsorption studies

EPA Science Inventory

Combustion synthesis of iron oxide/iron coated carbons such as activated carbon, anthracite, cellulose fiber and silica is described. The reactions were carried out in alumina crucibles using a Panasonic kitchen microwave with inverter technology, and the reaction process was com...

Characterization of Bending Magnetostriction in Iron-Gallium Alloys for Nanowire Sensor Applications

DTIC Science & Technology

2008-01-01

presence of an applied voltage. The pores that self assemble in a typical commercial batch of anodized alu- minum oxide ( AAO ) have only short range order...Moskovits. Magnetic properties of Fe deposited into anodic aluminum oxide pores as a function of particle size. J. Appl. Phys., 70:4421–4425, 1991. [96...The process begins by anodizing aluminum [92, 82] to produce porous tem- plates into which the nanowires can be grown. There are many recipes for the

[Blood detoxification using superparamagnetic nanoparticles (magnetic hemodialysis)].

PubMed

Ciochină, Al D; Untu, Alina; Iacob, Gh

2010-01-01

The authors present an experimental study realized in order to simulate blood detoxification with the help of supermagnetic nanoparticles. The particles used are red oxide nanoparticles which are considered to be equivalent from a magnetic susceptibility and dynamic diameter point of view to the complex structures of magnetite nanoparticles. Two types of custom HGMS matrices have been used--a threaded one and a micro-spheres one. For testing red oxide particles have been purposefully created to have a lower magnetic susceptibility than magnetite or iron-carbon particles used in other experimental studies. Different concentrations of iron oxide, glycerine and water have been prepared, creating a 3.5 cP viscosity (equivalent to the one of the blood); the concentrations of the prepared solutions varied between 0.16 mg/mL and 2 mg/mL, with the background magnetic field value ranging from 0.25 T to 0.9 T, in order to observer the effectiveness of filtering at different intensities. The efficiency of HGMS filtering in experimental conditions was almost completely successful (99.99%) in all experimental conditions, both with the threaded and micro-spheres matrices. The high gradient magnetic separation system of nanoparticles has maximum efficiency and has the potential of being implemented in a medical blood detoxification device.

Surface anisotropy of iron oxide nanoparticles and slabs from first principles: Influence of coatings and ligands as a test of the Heisenberg model

NASA Astrophysics Data System (ADS)

Brymora, Katarzyna; Calvayrac, Florent

2017-07-01

We performed ab initio computations of the magnetic properties of simple iron oxide clusters and slabs. We considered an iron oxide cluster functionalized by a molecule or glued to a gold cluster of the same size. We also considered a magnetite slab coated by cobalt oxide or a mixture of iron oxide and cobalt oxide. The changes in magnetic behavior were explored using constrained magnetic calculations. A possible value for the surface anisotropy was estimated from the fit of a classical Heisenberg model on ab initio results. The value was found to be compatible with estimations obtained by other means, or inferred from experimental results. The addition of a ligand, coating, or of a metallic nanoparticle to the systems degraded the quality of the description by the Heisenberg Hamiltonian. Proposing a change in the anisotropies allowing for the proportion of each transition atom we could get a much better description of the magnetism of series of hybrid cobalt and iron oxide systems.

Biofouling of contaminated ground-water recovery wells: Characterization of microorganisms

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

Taylor, S.W.; Lange, C.R.; Lesold, E.A.

1997-11-01

The taxonomy and physiology of microorganisms isolated from contaminated ground-water recovery wells prone to biofouling are characterized for an industrial site in Rochester, New York. Principal aquifer contaminants include acetone, cyclohexane, dichloroethane, dichloromethane, 1,4-dioxane, isopropanol, methanol, and toluene. These contaminants represent a significant fraction (up to 95%) of the total organic carbon in the ground water. Ground-water samples from 12 recovery wells were used to isolate, quantify, and identify aerobic and anaerobic bacterial populations. Samples from selected wells were also characterized geochemically to assess redox conditions and availability of essential and trace nutrients. Dominant bacteria, listed in order of descendingmore » numbers, including sulfate-reducers (Desulfovibrio desulfuricans), anaerobic heterotrophs (Actinomyces, Bacteriodes, Bacillus, Agrobacterium), aerobic heterotrophs (Pseudomonas, Flavobacterium, Nocardia, Citrobacter), iron-oxidizers (Gallionella ferruginea, Crenothrix polyspora), iron-reducers (Shewanella), and sulfur-oxidizers (Thiobacillus ferrooxidans). Fungi were also recovered in low numbers. Both aerobic and anaerobic heterotrophs were able to utilize all principal contaminants as sole carbon and energy sources except 1,4-dioxane. The prevalence of heterotrophic bacteria and their ability to use the available anthropogenic carbon suggests that aerobic and anaerobic heterotrophs contribute to the biofouling of wells at this site, in addition to the often cited fouling due to iron-oxidizing bacteria and sulfate-reducing bacteria.« less

Effect of surface charge on the colloidal stability and in vitro uptake of carboxymethyl dextran-coated iron oxide nanoparticles

PubMed Central

Ayala, Vanessa; Herrera, Adriana P.; Latorre-Esteves, Magda; Torres-Lugo, Madeline

2013-01-01

Nanoparticle physicochemical properties such as surface charge are considered to play an important role in cellular uptake and particle–cell interactions. In order to systematically evaluate the role of surface charge on the uptake of iron oxide nanoparticles, we prepared carboxymethyl-substituted dextrans with different degrees of substitution, ranging from 38 to 5 groups per chain, and reacted them using carbodiimide chemistry with amine–silane-coated iron oxide nanoparticles with narrow size distributions in the range of 33–45 nm. Surface charge of carboxymethyl-substituted dextran-coated nano-particles ranged from −50 to 5 mV as determined by zeta potential measurements, and was dependent on the number of carboxymethyl groups incorporated in the dextran chains. Nanoparticles were incubated with CaCo-2 human colon cancer cells. Nanoparticle–cell interactions were observed by confocal laser scanning microscopy and uptake was quantified by elemental analysis using inductively coupled plasma mass spectroscopy. Mechanisms of internalization were inferred using pharmacological inhibitors for fluid-phase, clathrin-mediated, and caveola-mediated endocytosis. Results showed increased uptake for nanoparticles with greater negative charge. Internalization patterns suggest that uptake of the most negatively charged particles occurs via non-specific interactions. PMID:24470787

Tuning the structure and habit of iron oxide mesocrystals

DOE PAGES

Wetterskog, Erik; Klapper, Alice; Disch, Sabrina; ...

2016-07-11

A precise control over the meso- and microstructure of ordered and aligned nanoparticle assemblies, i.e., mesocrystals, is essential in the quest for exploiting the collective material properties for potential applications. In this work, we produced evaporation-induced self-assembled mesocrystals with different mesostructures and crystal habits based on iron oxide nanocubes by varying the nanocube size and shape and by applying magnetic fields. A full 3D characterization of the mesocrystals was performed using image analysis, high-resolution scanning electron microscopy and Grazing Incidence Small Angle X-ray Scattering (GISAXS). This enabled the structural determination of e.g. multi-domain mesocrystals with complex crystal habits and themore » quantification of interparticle distances with sub-nm precision. Mesocrystals of small nanocubes (l = 8.6 12.6 nm) are isostructural with a body centred tetragonal (bct ) lattice whereas assemblies of the largest nanocubes in this study (l = 13.6 nm) additionally form a simple cubic (sc) lattice. The mesocrystal habit can be tuned from a square, hexagonal to star-like and pillar shapes depending on the particle size and shape and the strength of the applied magnetic field. Finally, we outline a qualitative phase diagram of the evaporation-induced self-assembled superparamagnetic iron oxide nanocube mesocrystals based on nanocube edge length and magnetic field strength.« less

Sorptive Uptake Studies of an Aryl-Arsenical with Iron Oxide Composites on an Activated Carbon Support

PubMed Central

Kwon, Jae H.; Wilson, Lee D.; Sammynaiken, Ramaswami

2014-01-01

Sorption uptake kinetics and equilibrium studies for 4-hydroxy-3-nitrobenzene arsonic acid (roxarsone) was evaluated with synthetic magnetite (Mag-P), commercial magnetite (Mag-C), magnetite 10%, 19%, and 32% composite material (CM-10, -19, -32) that contains granular activated carbon (GAC), and synthetic goethite at pH 7.00 in water at 21 °C for 24 h. GAC showed the highest sorptive removal of roxarsone and the relative uptake for each sorbent material with roxarsone are listed in descending order as follows: GAC (471 mg/g) > goethite (418 mg/g) > CM-10 (377 mg/g) CM-19 (254 mg/g) > CM-32 (227 mg/g) > Mag-P (132 mg/g) > Mag-C (29.5 mg/g). The As (V) moiety of roxarsone is adsorbed onto the surface of the iron oxide/oxyhydrate and is inferred as inner-sphere surface complexes; monodentate-mononuclear, bidentate-mononuclear, and bidentate-binuclear depending on the protolytic speciation of roxarsone. The phenyl ring of roxarsone provides the primary driving force for the sorptive interaction with the graphene surface of GAC and its composites. Thus, magnetite composites are proposed as multi-purpose adsorbents for the co-removal of inorganic and organic arsenicals due to the presence of graphenic and iron oxide active adsorption sites. PMID:28788545

Functional Gene Analysis of Freshwater Iron-Rich Flocs at Circumneutral pH and Isolation of a Stalk-Forming Microaerophilic Iron-Oxidizing Bacterium

PubMed Central

Chan, Clara; Itoh, Takashi; Ohkuma, Moriya

2013-01-01

Iron-rich flocs often occur where anoxic water containing ferrous iron encounters oxygenated environments. Culture-independent molecular analyses have revealed the presence of 16S rRNA gene sequences related to diverse bacteria, including autotrophic iron oxidizers and methanotrophs in iron-rich flocs; however, the metabolic functions of the microbial communities remain poorly characterized, particularly regarding carbon cycling. In the present study, we cultivated iron-oxidizing bacteria (FeOB) and performed clone library analyses of functional genes related to carbon fixation and methane oxidization (cbbM and pmoA, respectively), in addition to bacterial and archaeal 16S rRNA genes, in freshwater iron-rich flocs at groundwater discharge points. The analyses of 16S rRNA, cbbM, and pmoA genes strongly suggested the coexistence of autotrophic iron oxidizers and methanotrophs in the flocs. Furthermore, a novel stalk-forming microaerophilic FeOB, strain OYT1, was isolated and characterized phylogenetically and physiologically. The 16S rRNA and cbbM gene sequences of OYT1 are related to those of other microaerophilic FeOB in the family Gallionellaceae, of the Betaproteobacteria, isolated from freshwater environments at circumneutral pH. The physiological characteristics of OYT1 will help elucidate the ecophysiology of microaerophilic FeOB. Overall, this study demonstrates functional roles of microorganisms in iron flocs, suggesting several possible linkages between Fe and C cycling. PMID:23811518

Iron status and its relations with oxidative damage and bone loss during long-duration space flight on the International Space Station.

PubMed

Zwart, Sara R; Morgan, Jennifer L L; Smith, Scott M

2013-07-01

Increases in stored iron and dietary intake of iron during space flight have raised concern about the risk of excess iron and oxidative damage, particularly in bone. The objectives of this study were to perform a comprehensive assessment of iron status in men and women before, during, and after long-duration space flight and to quantify the association of iron status with oxidative damage and bone loss. Fasting blood and 24-h urine samples were collected from 23 crew members before, during, and after missions lasting 50 to 247 d to the International Space Station. Serum ferritin and body iron increased early in flight, and transferrin and transferrin receptors decreased later, which indicated that early increases in body iron stores occurred through the mobilization of iron to storage tissues. Acute phase proteins indicated no evidence of an inflammatory response during flight. Serum ferritin was positively correlated with the oxidative damage markers 8-hydroxy-2'-deoxyguanosine (r = 0.53, P < 0.001) and prostaglandin F2α (r = 0.26, P < 0.001), and the greater the area under the curve for ferritin during flight, the greater the decrease in bone mineral density in the total hip (P = 0.031), trochanter (P = 0.006), hip neck (P = 0.044), and pelvis (P = 0.049) after flight. Increased iron stores may be a risk factor for oxidative damage and bone resorption.

Microbial Iron Oxidation in the Arctic Tundra and Its Implications for Biogeochemical Cycling

PubMed Central

Scott, Jarrod J.; Benes, Joshua; Bowden, William B.

2015-01-01

The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long −149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. PMID:26386054

Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring.

PubMed

Kapuscinski, Martin; Agthe, Michael; Bergström, Lennart

2018-07-15

Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent-releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Hydrological tracers using nanobiotechnology: proof of concept.

PubMed

Sharma, Asha N; Luo, Dan; Walter, M Todd

2012-08-21

In order to answer questions that involve differentiating among multiple and potentially interacting hydrological flowpaths, it would be ideal to use multiple tracers with identical transport properties that can nonetheless be distinguished from each other. This paper describes the development and proof of concept of a new kind of engineered tracer system that allows a large number of individual tracers to be simultaneously distinguished from one another. This new tracer is composed of polylactic acid (PLA) microspheres into which short strands of synthetic DNA and paramagnetic iron oxide nanoparticles are incorporated. The synthetic DNA serves as the "label" or "tag" in our tracers that allow us to distinguish one tracer from another, and paramagnetic iron oxide nanoparticles are included in the tracer to facilitate magnetic concentration of the tracers in potentially dilute water samples. Some potential advantages of this tracer concept include: virtually limitless uniquely labeled tracers, highly sensitive detection, and relatively moderate expense. Three proof-of-concept experiments at scales ranging from orders of 10 cm to 100 m demonstrated the use of the tracer system.

Comparative genomic insights into ecophysiology of neutrophilic, microaerophilic iron oxidizing bacteria

DOE PAGES

Kato, Shingo; Ohkuma, Moriya; Powell, Deborah H.; ...

2015-11-13

Neutrophilic microaerophilic iron-oxidizing bacteria (FeOB) are thought to play a significant role in cycling of carbon, iron and associated elements in both freshwater and marine iron-rich environments. However, the roles of the neutrophilic microaerophilic FeOB are still poorly understood due largely to the difficulty of cultivation and lack of functional gene markers. Here, we analyze the genomes of two freshwater neutrophilic microaerophilic stalk-forming FeOB, Ferriphaselus amnicola OYT1 and Ferriphaselus strain R-1. Phylogenetic analyses confirm that these are distinct species within Betaproteobacteria; we describe strain R-1 and propose the name F. globulitus. We compare the genomes to those of two freshwatermore » Betaproteobacterial and three marine Zetaproteobacterial FeOB isolates in order to look for mechanisms common to all FeOB, or just stalk-forming FeOB. The OYT1 and R-1 genomes both contain homologs to cyc2, which encodes a protein that has been shown to oxidize Fe in the acidophilic FeOB, Acidithiobacillus ferrooxidans. This c-type cytochrome common to all seven microaerophilic FeOB isolates, strengthening the case for its common utility in the Fe oxidation pathway. In contrast, the OYT1 and R-1 genomes lack mto genes found in other freshwater FeOB. OYT1 and R-1 both have genes that suggest they can oxidize sulfur species. Both have the genes necessary to fix carbon by the Calvin–Benson– Basshom pathway, while only OYT1 has the genes necessary to fix nitrogen. The stalk-forming FeOB share xag genes that may help form the polysaccharide structure of stalks. Both OYT1 and R-1 make a novel biomineralization structure, short rod-shaped Fe oxyhydroxides much smaller than their stalks; these oxides are constantly shed, and may be a vector for C, P, and metal transport to downstream environments. Lastly, our results show that while different FeOB are adapted to particular niches, freshwater and marine FeOB likely share common mechanisms for Fe oxidation electron transport and biomineralization pathways.« less

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

PubMed

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

PubMed

Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

2011-12-06

The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

Identification of an iron permease, cFTR1, in cyanobacteria involved in the iron reduction/re-oxidation uptake pathway.

PubMed

Xu, Ning; Qiu, Guo-Wei; Lou, Wen-Jing; Li, Zheng-Ke; Jiang, Hai-Bo; Price, Neil M; Qiu, Bao-Sheng

2016-12-01

Cyanobacteria are globally important primary producers and abundant in many iron-limited aquatic environments. The ways in which they take up iron are largely unknown, but reduction of Fe 3+ is an important step in the process. Here we report a special iron permease in Synechocystis, cFTR1, that is required for Fe 3+ uptake following Fe 2+ re-oxidation. The expression of cFTR1 is induced by iron starvation, and a mutant lacking the gene is abnormally sensitive to iron starvation. The cFTR1 protein localizes to the plasma membrane and contains the iron-binding motif "REXXE". Point-directed mutagenesis of the REXXE motif results in a sensitivity to Fe-deficiency. Measurements of iron ( 55 Fe) uptake rate show that cFTR1 takes up Fe 3+ rather than Fe 2+ . The function of cFTR1 in Synechocystis could be genetically complemented by the iron permease, Ftr1p, of Saccharomyces cerevisiae, that is known to transport Fe 3+ produced by the oxidation of Fe 2+ via a multicopper oxidase. Unlike yeast Ftr1p, cyanobacterial cFTR1 probably obtains Fe 3+ primarily from the oxidation of Fe 2+ by oxygen. Growth assays show that the cFTR1 is required during oxygenic, photoautotrophic growth but not when oxygen production is inhibited during photoheterotrophic growth. In cyanobacteria, iron reduction/re-oxidation uptake pathway may represent their adaptation to oxygenated environments. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

PubMed

Woodman, Andrew G; Mah, Richard; Keddie, Danae; Noble, Ronan M N; Panahi, Sareh; Gragasin, Ferrante S; Lemieux, Hélène; Bourque, Stephane L

2018-06-01

Prenatal iron deficiency alters fetal developmental trajectories, which results in persistent changes in organ function. Here, we studied the effects of prenatal iron deficiency on fetal kidney and liver mitochondrial function. Pregnant Sprague-Dawley rats were fed partially or fully iron-restricted diets to induce a state of moderate or severe iron deficiency alongside iron-replete control rats. We assessed mitochondrial function via high-resolution respirometry and reactive oxygen species generation via fluorescence microscopy on gestational d 21. Hemoglobin levels were reduced in dams in the moderate (-31%) and severe groups (-54%) compared with controls, which was accompanied by 55% reductions in fetal hemoglobin levels in both moderate and severe groups versus controls. Male iron-deficient kidneys exhibited globally reduced mitochondrial content and respiration, as well as increased cytosolic superoxide and decreased NO. Female iron-deficient kidneys exhibited complex II down-regulation and increased mitochondrial oxidative stress. Male iron-deficient livers exhibited reduced complex IV respiration and increased cytosolic superoxide, whereas female liver tissues exhibited no alteration in oxidant levels or mitochondrial function. These findings indicate that prenatal iron deficiency causes changes in mitochondrial content and function as well as oxidant status in a sex- and organ-dependent manner, which may be an important mechanism that underlies the programming of cardiovascular disease.-Woodman, A. G., Mah, R., Keddie, D., Noble, R. M. N., Panahi, S., Gragasin, F. S., Lemieux, H., Bourque, S. L. Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

Labeling Efficacy of Superparamagnetic Iron Oxide Nanoparticles to Human Neural Stem Cells: Comparison of Ferumoxides, Monocrystalline Iron Oxide, Cross-linked Iron Oxide (CLIO)-NH2 and tat-CLIO

PubMed Central

Song, Miyeoun; Kim, Yunhee; Lim, Dongyeol; Song, In-Chan; Yoon, Byung-Woo

2007-01-01

Objective We wanted to compare the human neural stem cell (hNSC) labeling efficacy of different superparamagnetic iron oxide nanoparticles (SPIONs), namely, ferumoxides, monocrystalline iron oxide (MION), cross-linked iron oxide (CLIO)-NH2 and tat-CLIO. Materials and Methods The hNSCs (5 × 105 HB1F3 cells/ml) were incubated for 24 hr in cell culture media that contained 25 µg/ml of ferumoxides, MION or CLIO-NH2, and with or without poly-L-lysine (PLL) and tat-CLIO. The cellular iron uptake was analyzed qualitatively with using a light microscope and this was quantified via atomic absorption spectrophotometry. The visibility of the labeled cells was assessed with MR imaging. Results The incorporation of SPIONs into the hNSCs did not affect the cellular proliferations and viabilities. The hNSCs labeled with tat-CLIO showed the longest retention, up to 72 hr, and they contained 2.15 ± 0.3 pg iron/cell, which are 59 fold, 430 fold and six fold more incorporated iron than that of the hNSCs labeled with ferumoxides, MION or CLIO-NH2, respectively. However, when PLL was added, the incorporation of ferumoxides, MION or CLIO-NH2 into the hNSCs was comparable to that of tat-CLIO. Conclusion For MR imaging, hNSCs can be efficiently labeled with tat-CLIO alone or with a combination of ferumoxides, MION, CLIO-NH2 and the transfection agent PLL. PMID:17923778

A comparison of iron extraction methods for the determination of degree of pyritisation and the recognition of iron-limited pyrite formation

NASA Technical Reports Server (NTRS)

Raiswell, R.; Canfield, D. E.; Berner, R. A.

1994-01-01

Measurements of degree of pyritisation require an estimate of sediment iron which is capable of reaction with dissolved sulphide to form pyrite, either directly or indirectly via iron monosulphide precursors. Three dissolution techniques (buffered dithionite, cold 1 M HCl, boiling 12 M HCl) were examined for their capacity to extract iron from a variety of iron minerals, and iron-bearing sediments, as a function of different extraction times and different grain sizes. All the iron oxides studied are quantitatively extracted by dithionite and boiling HCl (but not by cold HCl). Both HCl techniques extract more iron from silicates than does dithionite but probably about the same amounts as are potentially capable of sulphidation. Modern sediment studies indicate that most sedimentary pyrite is formed rapidly from iron oxides, with smaller amounts formed more slowly from iron silicates (if sufficient geologic time is available). It is therefore recommended that the degree of pyritisation be defined with respect to the dithionite-extractable (mainly iron oxide) pool and/or the boiling HCl-extractable pool (which includes some silicate iron) for the recognition of iron-limited pyritisation.

Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?

NASA Astrophysics Data System (ADS)

Nuester, J.; Liermann, L. J.; Brantley, S. L.

2006-12-01

Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in significant iron isotope effects, and we are testing for these effects. For example, we expect to see enrichment of light isotopes in the early released fractions as iron is reduced (like effects observed by Wiederhold et al. (2006) for ligand-controlled and reductive dissolution of goethite). Such kinetic isotope effects should be particularly strong for iron release from siderophores with high Fe affinities like DFMB (log ß_(Fe(III)) = 30.60). We are also investigating other mechanisms to liberate iron from organic ligands including a pathway with extracellular iron reductases.

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.

Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

DOEpatents

Khan, M. Rashid

1989-01-01

A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis.

Targeted iron oxide nanoparticles for the enhancement of radiation therapy

PubMed Central

Hauser, Anastasia K.; Mitov, Mihail I.; Daley, Emily F.; McGarry, Ronald C.; Anderson, Kimberly W.; Hilt, J. Zach

2017-01-01

To increase the efficacy of radiation, iron oxide nanoparticles can be utilized for their ability to produce reactive oxygen species (ROS). Radiation therapy promotes leakage of electrons from the electron transport chain and leads to an increase in mitochondrial production of the superoxide anion which is converted to hydrogen peroxide by superoxide dismutase. Iron oxide nanoparticles can then catalyze the reaction from hydrogen peroxide to the highly reactive hydroxyl radical. Therefore, the overall aim of this project was to utilize iron oxide nanoparticles conjugated to a cell penetrating peptide, TAT, to escape lysosomal encapsulation after internalization by cancer cells and catalyze hydroxyl radical formation. It was determined that TAT functionalized iron oxide nanoparticles and uncoated iron oxide nanoparticles resulted in permeabilization of the lysosomal membranes. Additionally, mitochondrial integrity was compromised when A549 cells were treated with both TAT-functionalized nanoparticles and radiation. Pre-treatment with TAT-functionalized nanoparticles also significantly increased the ROS generation associated with radiation. A long term viability study showed that TAT-functionalized nanoparticles combined with radiation resulted in a synergistic combination treatment. This is likely due to the TAT-functionalized nanoparticles sensitizing the cells to subsequent radiation therapy, because the nanoparticles alone did not result in significant toxicities. PMID:27521615

Preparation, characterization and dynamical mechanical properties of dextran-coated iron oxide nanoparticles (DIONPs).

PubMed

Can, Hatice Kaplan; Kavlak, Serap; ParviziKhosroshahi, Shahed; Güner, Ali

2018-03-01

Dextran-coated iron oxide nanoparticles (DIONPs) with appropriate surface chemistry exhibit many interesting properties that can be exploited in a variety of biomedical applications such as magnetic resonance imaging (MRI) contrast enhancement, tissue repair, hyperthermia, drug delivery and in cell separation. This paper reports the experimental detail for preparation, characterization and investigation of thermal and dynamical mechanical characteristics of the dextran-coated Fe 3 O 4 magnetic nanoparticles. In our work, DIONPs were prepared in a 1:2 ratio of Fe(II) and Fe(III) salt in the HCl solution with NaOH at given temperature. The obtained dextran-coated iron-oxide nanoparticles structure-property correlation was characterized by spectroscopic methods; attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and XRD. Coating dextran on the iron-oxide proof of important peaks can be seen from the ATR-FTIR. Dramatic crystallinity increment can be observed from the XRD pattern of the iron-oxide dextran nanoparticles. The thermal analysis was examined by differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and differential thermal analysis (DTA). Dynamical mechanical properties of dextran nanoparticles were analysed by dynamic mechanical analysis (DMA). Thermal stability of the iron oxide dextran nanoparticles is higher than that of the dextran.

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.

Effect of soybean lecithin on iron-catalyzed or chlorophyll-photosensitized oxidation of canola oil emulsion.

PubMed

Choe, Jeesu; Oh, Boyoung; Choe, Eunok

2014-11-01

The effect of soybean lecithin addition on the iron-catalyzed or chlorophyll-photosensitized oxidation of emulsions consisting of purified canola oil and water (1:1, w/w) was studied based on headspace oxygen consumption using gas chromatography and hydroperoxide production using the ferric thiocyanate method. Addition levels of iron sulfate, chlorophyll, and soybean lecithin were 5, 4, and 350 mg/kg, respectively. Phospholipids (PLs) during oxidation of the emulsions were monitored by high performance liquid chromatography. Addition of soybean lecithin to the emulsions significantly reduced and decelerated iron-catalyzed oil oxidation by lowering headspace oxygen consumption and hydroperoxide production. However, soybean lecithin had no significant antioxidant effect on chlorophyll-photosensitized oxidation of the emulsions. PLs in soybean lecithin added to the emulsions were degraded during both oxidation processes, although there was little change in PL composition. Among PLs in soybean lecithin, phosphatidylethanolamine and phosphatidylinositol were degraded the fastest in the iron-catalyzed and the chlorophyll-photosensitized oxidation, respectively. The results suggest that addition of soybean lecithin as an emulsifier can also improve the oxidative stability of oil in an emulsion. © 2014 Institute of Food Technologists®

Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

DOEpatents

Clay, David T.; Lynn, Scott

1976-10-19

A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

Intracellular degradation of functionalized carbon nanotube/iron oxide hybrids is modulated by iron via Nrf2 pathway

PubMed Central

Elgrabli, Dan; Dachraoui, Walid; Marmier, Hélène de; Ménard-Moyon, Cécilia; Bégin, Dominique; Bégin-Colin, Sylvie; Bianco, Alberto; Alloyeau, Damien; Gazeau, Florence

2017-01-01

The in vivo fate and biodegradability of carbon nanotubes is still a matter of debate despite tremendous applications. In this paper we describe a molecular pathway by which macrophages degrade functionalized multi-walled carbon nanotubes (CNTs) designed for biomedical applications and containing, or not, iron oxide nanoparticles in their inner cavity. Electron microscopy and Raman spectroscopy show that intracellularly-induced structural damages appear more rapidly for iron-free CNTs in comparison to iron-loaded ones, suggesting a role of iron in the degradation mechanism. By comparing the molecular responses of macrophages derived from THP1 monocytes to both types of CNTs, we highlight a molecular mechanism regulated by Nrf2/Bach1 signaling pathways to induce CNT degradation via NOX2 complex activation and O2•−, H2O2 and OH• production. CNT exposure activates an oxidative stress-dependent production of iron via Nrf2 nuclear translocation, Ferritin H and Heme oxygenase 1 translation. Conversely, Bach1 was translocated to the nucleus of cells exposed to iron-loaded CNTs to recycle embedded iron. Our results provide new information on the role of oxidative stress, iron metabolism and Nrf2-mediated host defence for regulating CNT fate in macrophages. PMID:28120861

Recent developments in the formation and structure of tin-iron oxides by laser pyrolysis

NASA Astrophysics Data System (ADS)

Alexandrescu, R.; Morjan, I.; Dumitrache, F.; Birjega, R.; Fleaca, C.; Soare, I.; Gavrila, L.; Luculescu, C.; Prodan, G.; Kuncser, V.; Filoti, G.

2011-04-01

Complex oxides demonstrate specific electric and magnetic properties which make them suitable for a wide variety of applications, including dilute magnetic semiconductors for spin electronics. A tin-iron oxide Sn 1- xFe xO 2 nanoparticulate material has been successfully synthesized by using the laser pyrolysis of tetramethyl tin-iron pentacarbonyl-air mixtures. Fe doping of SnO 2 nanoparticles has been varied systematically in the 3-10 at% range. As determined by EDAX, the Fe/Sn ratio (in at%) in powders varied between 0.14 and 0.64. XRD studies of Sn 1- xFe xO 2 nanoscale powders, revealed only structurally modified SnO 2 due to the incorporation of Fe into the lattice mainly by substitutional changes. The substitution of Fe 3+ in the Sn 4+ positions (Fe 3+ has smaller ionic radius as compared to the ionic radius of 0.69 Å for Sn 4+) with the formation of a mixed oxide Sn 1- xFe xO 2 is suggested. A lattice contraction consistent with the determined Fe/Sn atomic ratios was observed. The nanoparticle size decreases with the Fe doping (about 7 nm for the highest Fe content). Temperature dependent 57Fe Mössbauer spectroscopy data point to the additional presence of defected Fe 3+-based oxide nanoclusters with blocking temperatures below 60 K. A new Fe phase presenting magnetic order at substantially higher temperatures was evidenced and assigned to a new type of magnetism relating to the dispersed Fe ions into the SnO 2 matrix.

Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite

NASA Technical Reports Server (NTRS)

Hung, Ching-cheh; McNatt, Jeremiah

2010-01-01

A document discusses a method for producing nanophase iron lunar dust composite simulant by heating a mixture of carbon black and current lunar simulant types (mixed oxide including iron oxide) at a high temperature to reduce ionic iron into elemental iron. The product is a chemically modified lunar simulant that can be attracted by a magnet, and has a surface layer with an iron concentration that is increased during the reaction. The iron was found to be -iron and Fe3O4 nanoparticles. The simulant produced with this method contains iron nanoparticles not available previously, and they are stable in ambient air. These nanoparticles can be mass-produced simply.

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.

Influence of Iron Oxide Particles on the Strength of Ball-Milled Iron

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

Lesuer, D R; Syn, C K; Sherby, O D

2005-12-07

Detailed microstructural and mechanical property studies of ball-milled iron, in the powder and consolidated states, are reviewed and assessed. The analyses cover three and one-half orders of magnitude of grain size (from 6 nm to 20 mm) and focus on the influence of oxide particles on the strength. The study includes the early work of Koch and Yang, Kimura and Takaki and continues with the more recent work of Umemoto et al and Belyakov, Sakai et al. It is shown that the major contributors to strength are the nanooxide particles. These particles are created by adiabatic shear banding during ball-millingmore » leading to a bimodal distribution of particles. The predicted strength from particles, {sigma}{sub p}, is given by {sigma}{sub p} = B {center_dot} (D*{sub S}){sup -1/2} where D*{sub S} is the surface-to-surface interparticle spacing, and B = 395 MPa {center_dot} {micro}m{sup -1/2}. A model is proposed that accounts for the influence of the bimodal particle size distribution on strength.« less

Iron oxide nanoparticles in geomicrobiology: from biogeochemistry to bioremediation.

PubMed

Braunschweig, Juliane; Bosch, Julian; Meckenstock, Rainer U

2013-09-25

Iron oxides are important constituents of soils and sediments and microbial iron reduction is considered to be a significant anaerobic respiration process in the subsurface, however low microbial reduction rates of macroparticulate Fe oxides in laboratory studies led to an underestimation of the role of Fe oxides in the global Fe redox cycle. Recent studies show the high potential of nano-sized Fe oxides in the environment as, for example, electron acceptor for microbial respiration, electron shuttle between different microorganisms, and scavenger for heavy metals. Biotic and abiotic reactivity of iron macroparticles differ significantly from nano-sized Fe oxides, which are usually much more reactive. Factors such as particle size, solubility, ferrous iron, crystal structure, and organic molecules were identified to influence the reactivity. This review discusses factors influencing the microbial reactivity of Fe oxides. It highlights the differences between natural and synthetic Fe oxides especially regarding the presence of organic molecules such as humic acids and natural organic matter. Attention is given to the transport behavior of Fe oxides in laboratory systems and in the environment, because of the high affinity of different contaminants to Fe oxide surfaces and associated co-transport of pollutants. The high reactivity of Fe oxides and their potential as adsorbents for different pollutants are discussed with respect to application and development of remediation technologies. Copyright © 2013. Published by Elsevier B.V.

Salt Stress-Induced Loss of Iron Oxidoreduction Activities and Reacquisition of That Phenotype Depend on rus Operon Transcription in Acidithiobacillus ferridurans.

PubMed

Bonnefoy, Violaine; Grail, Barry M; Johnson, D Barrie

2018-04-01

The type strain of the mineral-oxidizing acidophilic bacterium Acidithiobacillus ferridurans was grown in liquid medium containing elevated concentrations of sodium chloride with hydrogen as electron donor. While it became more tolerant to chloride, after about 1 year, the salt-stressed acidophile was found to have lost its ability to oxidize iron, though not sulfur or hydrogen. Detailed molecular examination revealed that this was due to an insertion sequence, IS Afd1 , which belongs to the IS Pepr1 subgroup of the IS 4 family, having been inserted downstream of the two promoters PI and PII of the rus operon (which codes for the iron oxidation pathway in this acidophile), thereby preventing its transcription. The ability to oxidize iron was regained on protracted incubation of the culture inoculated onto salt-free solid medium containing ferrous iron and incubated under hydrogen. Two revertant strains were obtained. In one, the insertion sequence IS Afd1 had been excised, leaving an 11-bp signature, while in the other an ∼2,500-bp insertion sequence (belonging to the IS 66 family) was detected in the downstream inverted repeat of IS Afd1 The transcriptional start site of the rus operon in the second revertant strain was downstream of the two ISs, due to the creation of a new "hybrid" promoter. The loss and subsequent regaining of the ability of A. ferridurans T to reduce ferric iron were concurrent with those observed for ferrous iron oxidation, suggesting that these two traits are closely linked in this acidophile. IMPORTANCE Iron-oxidizing acidophilic bacteria have primary roles in the oxidative dissolution of sulfide minerals, a process that underpins commercial mineral-processing biotechnologies ("biomining"). Most of these prokaryotes have relatively low tolerance to chloride, which limits their activities when only saline or brackish waters are available. The study showed that it was possible to adapt a typical iron-oxidizing acidophile to grow in the presence of salt concentrations similar to those in seawater, but in so doing they lost their ability to oxidize iron, though not sulfur or hydrogen. The bacterium regained its capacity for oxidizing iron when the salt stress was removed but simultaneously reverted to tolerating lower concentrations of salt. These results suggest that the bacteria that have the main roles in biomining operations could survive but become ineffective in cases where saline or brackish waters are used for irrigation. Copyright © 2018 American Society for Microbiology.

Alginate-Iron Speciation and Its Effect on In Vitro Cellular Iron Metabolism

PubMed Central

Horniblow, Richard D.; Dowle, Miriam; Iqbal, Tariq H.; Latunde-Dada, Gladys O.; Palmer, Richard E.

2015-01-01

Alginates are a class of biopolymers with known iron binding properties which are routinely used in the fabrication of iron-oxide nanoparticles. In addition, alginates have been implicated in influencing human iron absorption. However, the synthesis of iron oxide nanoparticles employs non-physiological pH conditions and whether nanoparticle formation in vivo is responsible for influencing cellular iron metabolism is unclear. Thus the aims of this study were to determine how alginate and iron interact at gastric-comparable pH conditions and how this influences iron metabolism. Employing a range of spectroscopic techniques under physiological conditions alginate-iron complexation was confirmed and, in conjunction with aberration corrected scanning transmission electron microscopy, nanoparticles were observed. The results infer a nucleation-type model of iron binding whereby alginate is templating the condensation of iron-hydroxide complexes to form iron oxide centred nanoparticles. The interaction of alginate and iron at a cellular level was found to decrease cellular iron acquisition by 37% (p < 0.05) and in combination with confocal microscopy the alginate inhibits cellular iron transport through extracellular iron chelation with the resulting complexes not internalised. These results infer alginate as being useful in the chelation of excess iron, especially in the context of inflammatory bowel disease and colorectal cancer where excess unabsorbed luminal iron is thought to be a driver of disease. PMID:26378798

Milk protein composition and stability changes affected by iron in water sources.

PubMed

Wang, Aili; Duncan, Susan E; Knowlton, Katharine F; Ray, William K; Dietrich, Andrea M

2016-06-01

Water makes up more than 80% of the total weight of milk. However, the influence of water chemistry on the milk proteome has not been extensively studied. The objective was to evaluate interaction of water-sourced iron (low, medium, and high levels) on milk proteome and implications on milk oxidative state and mineral content. Protein composition, oxidative stability, and mineral composition of milk were investigated under conditions of iron ingestion through bovine drinking water (infused) as well as direct iron addition to commercial milk in 2 studies. Four ruminally cannulated cows each received aqueous infusions (based on water consumption of 100L) of 0, 2, 5, and 12.5mg/L Fe(2+) as ferrous lactate, resulting in doses of 0, 200, 500 or 1,250mg of Fe/d, in a 4×4Latin square design for a 14-d period. For comparison, ferrous sulfate solution was directly added into commercial retail milk at the same concentrations: control (0mg of Fe/L), low (2mg of Fe/L), medium (5mg of Fe/L), and high (12.5mg of Fe/L). Two-dimensional electrophoresis coupled with matrix-assisted laser desorption/ionization-tandem time-of-flight (MALDI-TOF/TOF) high-resolution tandem mass spectrometry analysis was applied to characterize milk protein composition. Oxidative stability of milk was evaluated by the thiobarbituric acid reactive substances (TBARS) assay for malondialdehyde, and mineral content was measured by inductively coupled plasma mass spectrometry. For milk from both abomasal infusion of ferrous lactate and direct addition of ferrous sulfate, an iron concentration as low as 2mg of Fe/L was able to cause oxidative stress in dairy cattle and infused milk, respectively. Abomasal infusion affected both caseins and whey proteins in the milk, whereas direct addition mainly influenced caseins. Although abomasal iron infusion did not significantly affect oxidation state and mineral balance (except iron), it induced oxidized off-flavor and partial degradation of whey proteins. Direct iron addition to milk led to lipid oxidation during storage at 4°C. Oxidation level was positively associated with the concentration of added iron. Minerals (Mg, P, Na, K, Ca, Zn) in milk were not affected by the added iron in milk. This study indicated that a small amount of iron contamination in bovine drinking water at the farm or incidental iron addition from potable water sources causes oxidation, affects milk protein composition and stability, and affects final milk quality. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Study of Nanodispersed Iron Oxides Produced in Steel Drilling by Contracted Electric-Arc Air Plasma Torch

NASA Astrophysics Data System (ADS)

Stefanov, P.; Galanov, D.; Vissokov, G.; Paneva, D.; Kunev, B.; Mitov, I.

2008-06-01

The optimal conditions on the plasma-forming gas flowrate, discharge current and voltage, distance between the plasma-torch nozzle and the metal plate surface for the process of penetration in and vaporization of steel plates by the contracted electric-arc air plasma torch accompanied by water quenching, were determined. The X-ray structural and phase studies as well as Mössbauer and electron microscope studies on the samples treated were performed. It was demonstrated that the vaporized elemental iron was oxidized by the oxygen present in the air plasma jet to form iron oxides (wüstite, magnetite, hematite), which, depending on their mass ratios, determined the color of the iron oxide pigments, namely, beginning from light yellow, through deep yellow, light brown, deep brown, violet, red-violet, to black. A high degree of dispersity of the iron oxides is thus produced, with an averaged diameter of the particles below 500 nm, and their defective crystal structure form the basis of their potential application as components of iron-containing catalysts and pigments.

Liquid Phase Plasma Synthesis of Iron Oxide Nanoparticles on Nitrogen-Doped Activated Carbon Resulting in Nanocomposite for Supercapacitor Applications.

PubMed

Lee, Heon; Lee, Won-June; Park, Young-Kwon; Ki, Seo Jin; Kim, Byung-Joo; Jung, Sang-Chul

2018-03-25

Iron oxide nanoparticles supported on nitrogen-doped activated carbon powder were synthesized using an innovative plasma-in-liquid method, called the liquid phase plasma (LPP) method. Nitrogen-doped carbon (NC) was prepared by a primary LPP reaction using an ammonium chloride reactant solution, and an iron oxide/NC composite (IONCC) was prepared by a secondary LPP reaction using an iron chloride reactant solution. The nitrogen component at 3.77 at. % formed uniformly over the activated carbon (AC) surface after a 1 h LPP reaction. Iron oxide nanoparticles, 40~100 nm in size, were impregnated homogeneously over the NC surface after the LPP reaction, and were identified as Fe₃O₄ by X-ray photoelectron spectroscopy and X-ray diffraction. NC and IONCCs exhibited pseudo-capacitive characteristics, and their specific capacitance and cycling stability were superior to those of bare AC. The nitrogen content on the NC surface increased the compatibility and charge transfer rate, and the composites containing iron oxide exhibited a lower equivalent series resistance.

Microwave-assisted synthesis of carbon supported metal/metal oxide nanocomposites and their application in water purification

NASA Astrophysics Data System (ADS)

Gunawan, Gunawan

A novel, easy, and cost effective method for synthesizing carbon supported metal/metal oxide nanocomposites has been studied. Carbon supported metal/metal oxide nanocomposites have niche applications in the area of catalysis, fuel cells, electrodes, and more. The method utilizes a commercial microwave and features the addition of a developed graphite-jacket technique with renewable carbon resources, tannin and lignin. The method has been successfully used to synthesize carbon/nickel, carbon/iron oxide, and carbon/nickel phosphide nanocomposites. The method has shown its versatility in the synthesis of carbon nanocomposites. The process is much simpler when compared with the available methods for synthesizing carbon nanocomposites. The synthesized nanocomposites were classified using several characterization techniques, such as electron microscopy, X-ray powder diffraction, surface area analysis, thermogravimetric analysis, and spectrophotometric studies. One application of the carbon nanocomposite is in wastewater remediation. The synthesized carbon/iron oxide nanocomposite was noted as being useful for removing arsenic (As) and phosphorus (P) from contaminated water. The adsorption process of the nanocomposite was critically studied in order to understand the process of removing pollutants from contaminated water. The study shows that the nanocomposites are capable of removing As and P from contaminated water. Kinetic and adsorption isotherm studies were applied to understand the adsorption of As and P onto the adsorbent. Several methods, such as pseudo-first and second order kinetic models, Elovich's equation, and the Weber-Morris intraparticle diffusion model were used to explain the kinetic aspects of the adsorption process. For the adsorption isotherm study, Langmuir and Freundlich isotherm models were applied.

Ligand-Enhanced Abiotic Iron Oxidation and the Effects of Chemical versus Biological Iron Cycling in Anoxic Environments

PubMed Central

2013-01-01

This study introduces a newly isolated, genetically tractable bacterium (Pseudogulbenkiania sp. strain MAI-1) and explores the extent to which its nitrate-dependent iron-oxidation activity is directly biologically catalyzed. Specifically, we focused on the role of iron chelating ligands in promoting chemical oxidation of Fe(II) by nitrite under anoxic conditions. Strong organic ligands such as nitrilotriacetate and citrate can substantially enhance chemical oxidation of Fe(II) by nitrite at circumneutral pH. We show that strain MAI-1 exhibits unambiguous biological Fe(II) oxidation despite a significant contribution (∼30–35%) from ligand-enhanced chemical oxidation. Our work with the model denitrifying strain Paracoccus denitrificans further shows that ligand-enhanced chemical oxidation of Fe(II) by microbially produced nitrite can be an important general side effect of biological denitrification. Our assessment of reaction rates derived from literature reports of anaerobic Fe(II) oxidation, both chemical and biological, highlights the potential competition and likely co-occurrence of chemical Fe(II) oxidation (mediated by microbial production of nitrite) and truly biological Fe(II) oxidation. PMID:23402562

Stability of oxidized iron species and the redox budget of slab-derived fluids

NASA Astrophysics Data System (ADS)

Sanchez-Valle, C.; Hin, R.; Testemale, D.; Borca, C.; Grolimund, D.

2017-12-01

The high oxidation state of subduction zone magmas compared to magmas from other locations might result from the influx of oxidized fluid from the subducted oceanic plate into the mantle wedge. However, the nature of the chemical agent(s) and the mechanism responsible for the transfer of the oxidized signature from the slab to the mantle wedge remains poorly understood. In this contribution, we will discuss the oxidizing capacity of slab-derived fluids in the light of experimental results of the solubility and speciation of iron in high-pressure fluids that mimic the slab flux. Iron-bearing mineral assemblages were equilibrated with chlorinated aqueous fluids and hydrous granitic melts at different oxygen fugacities relevant for the present day crust/mantle. The concentration of iron and the distribution of stability of oxidized iron species were monitored up to 2.5 GPa and 800 °C using a combination of diamond trap experiments and XANES measurements in diamond anvil cells. The results illustrate the role of coordination chemistry involving halogen and polymerized species in the stability of oxidized iron in the fluids. The concentration of Fe3+ in the fluids progressively decreases as temperature increases, regardless of fluid composition and pressure. This implies that the fluid capacity to transport Fe3+ at high temperature may be limited, even at the redox conditions relevant for the present day crust and mantle. With the new experimental results, we place constrains on the oxidizing capacity of Fe-bearing metasomatic fluids and discuss the transfer of the oxidizing signature and the conditions for the genesis of oxidized arc magmas.

Iron oxides in human spleen.

PubMed

Kopáni, Martin; Miglierini, Marcel; Lančok, Adriana; Dekan, Július; Čaplovicová, Mária; Jakubovský, Ján; Boča, Roman; Mrazova, Hedviga

2015-10-01

Iron is an essential element for fundamental cell functions and a catalyst for chemical reactions. Three samples extracted from the human spleen were investigated by scanning (SEM) and transmission electron microscopy (TEM), Mössbauer spectrometry (MS), and SQUID magnetometry. The sample with diagnosis of hemosiderosis (H) differs from that referring to hereditary spherocytosis and the reference sample. SEM reveals iron-rich micrometer-sized aggregate of various structures-tiny fibrils in hereditary spherocytosis sample and no fibrils in hemochromatosis. Hematite and magnetite particles from 2 to 6 μm in TEM with diffraction in all samples were shown. The SQUID magnetometry shows different amount of diamagnetic, paramagnetic and ferrimagnetic structures in the tissues. The MS results indicate contribution of ferromagnetically split sextets for all investigated samples. Their occurrence indicates that at least part of the sample is magnetically ordered below the critical temperature. The iron accumulation process is different in hereditary spherocytosis and hemosiderosis. This fact may be the reason of different iron crystallization.

Oxidation Character of Carbon Composite Bricks Used in Blast Furnace

NASA Astrophysics Data System (ADS)

Zuo, Haibin; Wang, Cong; Zhang, Jianliang; Jiao, Kexin; Zhao, Yongan

The carbon composite brick is a new refractory used in blast furnace hearth and bottom. It caused wide attention due to its high thermal conductivity and low erosion by molten iron. In this paper, chemical constituents, SEM-EDS and X-ray diffraction were carried out in order to understand reaction mechanisms. A series of experiments of oxidation resistance characteristics were made. The oxidation mechanisms of carbon composite bricks in the presence of air were analyzed. According to the analysis on many experimental results, the oxidation process of carbon composite bricks under different temperatures were controlled by different mechanisms. In the condition of high temperature, SiO2 as oxidation product hindered the diffusion of O2, and reduced the oxidation loss of graphite in the internal.

Microbial Anaerobic Ammonium Oxidation Under Iron Reducing Conditions, Alternative Electron Acceptors

NASA Astrophysics Data System (ADS)

Ruiz-Urigüen, M.; Jaffe, P. R.

2015-12-01

Autotrophic Acidimicrobiaceae-bacterium named A6 (A6), part of the Actinobacteria phylum have been linked to anaerobic ammonium (NH4+) oxidation under iron reducing conditions. These organisms obtain their energy by oxidizing NH4+ and transferring the electrons to a terminal electron acceptor (TEA). Under environmental conditions, the TEAs are iron oxides [Fe(III)], which are reduced to Fe(II), this process is known as Feammox. Our studies indicate that alternative forms of TEAs can be used by A6, e.g. iron rich clays (i.e. nontronite) and electrodes in bioelectrochemical systems such as Microbial Electrolysis Cells (MECs), which can sustain NH4+removal and A6 biomass production. Our results show that nontronite can support Feammox and promote bacterial cell production. A6 biomass increased from 4.7 x 104 to 3.9 x 105 cells/ml in 10 days. Incubations of A6 in nontronite resulted in up to 10 times more NH4+ removal and 3 times more biomass production than when ferrihydrite is used as the Fe(III) source. Additionally, Fe in nontronite can be reoxidized by aeration and A6 can reutilize it; however, Fe is still finite in the clay. In contrast, in MECs, A6 harvest electrons from NH4+ and use an anode as an unlimited TEA, as a result current is produced. We operated multiple MECs in parallel using a single external power source, as described by Call & Logan (2011). MECs were run with an applied voltage of 0.7V and different growing mediums always containing initial 5mM NH4+. Results show that current production is favored when anthraquinone-2,6-disulfonate (AQDS), an electron shuttled, is present in the medium as it facilitates the transfer of electrons from the bacterial cell to the anode. Additionally, A6 biomass increased from 1 x 104 to 9.77 x 105cells/ml in 14 days of operation. Due to Acidimicrobiaceae-bacterium A6's ability to use various TEAs, MECs represent an alternative, iron-free form, for optimized biomass production of A6 and its application in NH4+ oxidation, an essential process in water quality control. Future work seeks to scale up MECs in order to achieve rates of microbial NH4+ oxidation comparable to existing technologies.

Activation of Hydrogen Peroxide by Iron-Containing Minerals and Catalysts in Circumneutral pH Solutions: Implications for ex situ and in situ Treatment of Contaminated Water and Soil

NASA Astrophysics Data System (ADS)

Pham, Anh Le Tuan

The decomposition of hydrogen peroxide (H2O2) on iron minerals can generate hydroxyl radical (•OH), a strong oxidant capable of transforming a wide range of contaminants. This reaction is critical to ex situ advanced oxidation processes employed in waste treatment systems, as well as in situ chemical oxidation processes used for soil and groundwater remediation. Unfortunately, the process in the ex situ treatment systems is relatively inefficient at circumneutral pH values. In this research, the development of iron-containing catalysts with improved efficiency was investigated. In addition, little is known about the factors that control the performance of in situ treatment systems. Another aim of this dissertation was to elucidate those factors to provide a basis for improving the efficiency of the remediation method. Two types of silica- and alumina-containing iron (hydr)oxide catalysts were synthesized by sol-gel processing techniques (Chapter 2). Relative to iron oxides, such as hematite and goethite, these catalysts were 10 to 80 times more effective in catalyzing the production of •OH from H2O2 under circumneutral conditions. The higher efficiency makes these catalysts promising candidates for ex situ advanced oxidation processes. Moreover, because alumina and silica alter the reactivity of the iron oxides with H2O2, understanding the activity of iron associated with natural aluminosilicates and silica-containing minerals in the subsurface is crucial to explaining the variability of •OH production observed in in situ treatment systems. In addition to the sol-gel technique used in Chapter 2, silica-containing iron (hydr)oxide catalysts were synthesized by immobilizing iron oxide onto mesoporous silica supports, such as SBA-15 (Chapter 5). The iron-containing SBA-15 was 10 times more effective than iron oxides in catalyzing the production of •OH from H2O2. Moreover, this catalyst could be employed for selective oxidation of small organic contaminants based on size exclusion. However, a major drawback of the mesoporous silica-based catalysts is their instability under circumneutral conditions (Chapter 6). The dissolution of mesoporous silica materials raises questions about their use for water treatment, because silica dissolution might compromise the behavior of the material. To gain insight into factors that control H2O2 persistence and •OH yield in in situ processes, the decomposition of H2O2 and transformation of contaminants were investigated in the presence of iron-containing minerals and aquifer materials (Chapter 3). Consistent with the observation described in Chapter 2, iron-containing aluminosilicates were more effective than iron oxides in converting H2O2 into •OH. In both iron-containing mineral and aquifer material systems, the yield of •OH was inversely correlated with the rate of H 2O2 decomposition. In the aquifer material systems, the yield also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce •OH. The inverse correlation between Mn content and H2O2 loss rate and •OH yield suggests that the amount of Mn in aquifer materials could serve as a proxy for predicting H2O2 decomposition rates and contaminant oxidation efficiency. In addition to the surface and structure properties of iron solids, the presence of solutes, such as dissolved silica, also affected the decomposition of H2O2 (Chapter 4). The adsorption of dissolved silica onto mineral surfaces altered the catalytic sites, thereby decreasing the reactivity of iron- and manganese-containing minerals with H2O 2. Therefore, the presence of dissolved SiO2 could lead to greater persistence of H2O2 in groundwater, which should be considered in the design of in situ H2O 2-based treatment systems. In addition to in situ treatment, dissolved silica also can affect the reactivity of iron-containing catalysts used in ex situ processes. Therefore, its presence in contaminated industrial wastewater should be considered when ex situ treatment systems are designed.

The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

PubMed Central

Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

2017-01-01

The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the −35 (or −24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed. PMID:28747899

Intra-puff CO and CO 2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

NASA Astrophysics Data System (ADS)

Crawford, Danielle R.; Parrish, Milton E.; Gee, Diane L.; Harward, Charles N.

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO 2 as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1 s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO 2 intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO 2 deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy.

PubMed

Crawford, Danielle R; Parrish, Milton E; Gee, Diane L; Harward, Charles N

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Microarray analysis of Pseudomonas aeruginosa reveals induction of pyocin genes in response to hydrogen peroxide

PubMed Central

Chang, Wook; Small, David A; Toghrol, Freshteh; Bentley, William E

2005-01-01

Background Pseudomonas aeruginosa, a pathogen infecting those with cystic fibrosis, encounters toxicity from phagocyte-derived reactive oxidants including hydrogen peroxide during active infection. P. aeruginosa responds with adaptive and protective strategies against these toxic species to effectively infect humans. Despite advances in our understanding of the responses to oxidative stress in many specific cases, the connectivity between targeted protective genes and the rest of cell metabolism remains obscure. Results Herein, we performed a genome-wide transcriptome analysis of the cellular responses to hydrogen peroxide in order to determine a more complete picture of how oxidative stress-induced genes are related and regulated. Our data reinforce the previous conclusion that DNA repair proteins and catalases may be among the most vital antioxidant defense systems of P. aeruginosa. Our results also suggest that sublethal oxidative damage reduces active and/or facilitated transport and that intracellular iron might be a key factor for a relationship between oxidative stress and iron regulation. Perhaps most intriguingly, we revealed that the transcription of all F-, R-, and S-type pyocins was upregulated by oxidative stress and at the same time, a cell immunity protein (pyocin S2 immunity protein) was downregulated, possibly leading to self-killing activity. Conclusion This finding proposes that pyocin production might be another novel defensive scheme against oxidative attack by host cells. PMID:16150148

Zur (FurB) is a key factor in the control of the oxidative stress response in Anabaena sp. PCC 7120.

PubMed

Sein-Echaluce, Violeta C; González, Andrés; Napolitano, Mauro; Luque, Ignacio; Barja, Francisco; Peleato, M Luisa; Fillat, María F

2015-06-01

Iron and zinc are necessary nutrients whose homeostasis is tightly controlled by members of the ferric uptake regulator (FUR) superfamily in the cyanobacterium Anabaena sp. PCC7120. Although the link between iron metabolism and oxidative stress management is well documented, little is known about the connection between zinc homeostasis and the oxidative stress response in cyanobacteria. Zinc homeostasis in Anabaena is controlled by Zur, also named FurB. When overexpressed in Escherichia coli, Zur (FurB) improved cell survival during oxidative stress. In order to investigate the possible correlation between Zur and the oxidative stress response in Anabaena, zur deletion and zur-overexpressing strains have been constructed, and the consequences of Zur imbalance evaluated. The lack of Zur increased sensitivity to hydrogen peroxide (H2 O2 ), whereas an excess of Zur enhanced oxidative stress resistance. Both mutants displayed pleiotropic phenotypes, including alterations on the filament surfaces observable by scanning electron microscopy, reduced content of endogenous H2 O2 and altered expression of sodA, catalases and several peroxiredoxins. Transcriptional and biochemical analyses unveiled that the appropriate level of Zur is required for proper control of the oxidative stress response and allowed us to identify major antioxidant enzymes as novel members of the Zur regulon. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Remediation of TCE-contaminated groundwater using acid/BOF slag enhanced chemical oxidation.

PubMed

Tsai, T T; Kao, C M; Wang, J Y

2011-04-01

The objective of this study was to evaluate the potential of applying acid/H(2)O(2)/basic oxygen furnace slag (BOF slag) and acid/S(2)O(8)(2-)/BOF slag systems to enhance the chemical oxidation of trichloroethylene (TCE)-contaminated groundwater. Results from the bench-scale study indicate that TCE oxidation via the Fenton-like oxidation process can be enhanced with the addition of BOF slag at low pH (pH=2-5.2) and neutral (pH=7.1) conditions. Because the BOF slag has iron abundant properties (14% of FeO and 6% of Fe(2)O(3)), it can be sustainably reused for the supplement of iron minerals during the Fenton-like or persulfate oxidation processes. Results indicate that higher TCE removal efficiency (84%) was obtained with the addition of inorganic acid for the activation of Fenton-like reaction compared with the experiments with organic acids addition (with efficiency of 10-15% lower) (BOF slag=10gL(-1); initial pH=5.2). This could be due to the fact that organic acids would compete with TCE for available oxidants. Results also indicate that the pH value had a linear correlation with the observed first-order decay constant of TCE, and thus, lower pH caused a higher TCE oxidation rate. Copyright © 2011 Elsevier Ltd. All rights reserved.

Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI.

PubMed

Kim, Cheolyong; Ahn, Jun-Young; Kim, Tae Yoo; Shin, Won Sik; Hwang, Inseong

2018-03-20

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction

PubMed Central

Sastri, Chivukula V.; Lee, Jimin; Oh, Kyungeun; Lee, Yoon Jin; Lee, Junghyun; Jackson, Timothy A.; Ray, Kallol; Hirao, Hajime; Shin, Woonsup; Halfen, Jason A.; Kim, Jinheung; Que, Lawrence; Shaik, Sason; Nam, Wonwoo

2007-01-01

The reactivities of mononuclear nonheme iron(IV)–oxo complexes bearing different axial ligands, [FeIV(O)(TMC)(X)]n+ [where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and X is NCCH3 (1-NCCH3), CF3COO− (1-OOCCF3), or N3− (1-N3)], and [FeIV(O)(TMCS)]+ (1′-SR) (where TMCS is 1-mercaptoethyl-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane), have been investigated with respect to oxo-transfer to PPh3 and hydrogen atom abstraction from phenol OH and alkylaromatic CH bonds. These reactivities were significantly affected by the identity of the axial ligands, but the reactivity trends differed markedly. In the oxidation of PPh3, the reactivity order of 1-NCCH3 > 1-OOCCF3 > 1-N3 > 1′-SR was observed, reflecting a decrease in the electrophilicity of iron(IV)–oxo unit upon replacement of CH3CN with an anionic axial ligand. Surprisingly, the reactivity order was inverted in the oxidation of alkylaromatic CH and phenol OH bonds, i.e., 1′-SR > 1-N3 > 1-OOCCF3 > 1-NCCH3. Furthermore, a good correlation was observed between the reactivities of iron(IV)–oxo species in H atom abstraction reactions and their reduction potentials, Ep,c, with the most reactive 1′-SR complex exhibiting the lowest potential. In other words, the more electron-donating the axial ligand is, the more reactive the iron(IV)–oxo species becomes in H atom abstraction. Quantum mechanical calculations show that a two-state reactivity model applies to this series of complexes, in which a triplet ground state and a nearby quintet excited-state both contribute to the reactivity of the complexes. The inverted reactivity order in H atom abstraction can be rationalized by a decreased triplet-quintet gap with the more electron-donating axial ligand, which increases the contribution of the much more reactive quintet state and enhances the overall reactivity. PMID:18048327

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

PubMed Central

Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

2013-01-01

Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

The nanosphere iron mineral(s) in Mars soil

NASA Technical Reports Server (NTRS)

Banin, A.; Ben-Shlomo, T.; Margulies, L.; Blake, D. F.; Mancinelli, R. L.; Gehring, A. U.

1993-01-01

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Iron accumulates in the lavage and explanted lungs of cystic fibrosis patients.

EPA Science Inventory

Abstract Oxidative stress participates in the pathophysiology of cystic fibrosis (CF). An underlying disruption in iron homeostasis can frequently be demonstrated in injuries and diseases associated with an oxidative stress. We tested the hypothesis that iron accumulation and ...

Diverse arsenic- and iron-cycling microbial communities in arsenic-contaminated aquifers used for drinking water in Bangladesh.

PubMed

Hassan, Zahid; Sultana, Munawar; van Breukelen, Boris M; Khan, Sirajul I; Röling, Wilfred F M

2015-04-01

Subsurface removal of arsenic by injection with oxygenated groundwater has been proposed as a viable technology for obtaining 'safe' drinking water in Bangladesh. While the oxidation of ferrous iron to solid ferric iron minerals, to which arsenic adsorbs, is assumed to be driven by abiotic reactions, metal-cycling microorganisms may potentially affect arsenic removal. A cultivation-independent survey covering 24 drinking water wells in several geographical regions in Bangladesh was conducted to obtain information on microbial community structure and diversity in general, and on specific functional groups capable of the oxidation or reduction of arsenic or iron. Each functional group, targeted by either group-specific 16S rRNA or functional gene amplification, occurred in at least 79% of investigated samples. Putative arsenate reducers and iron-oxidizing Gallionellaceae were present at low diversity, while more variation in potentially arsenite-oxidizing microorganisms and iron-reducing Desulfuromonadales was revealed within and between samples. Relations between community composition on the one hand and hydrochemistry on the other hand were in general not evident, apart from an impact of salinity on iron-cycling microorganisms. Our data suggest widespread potential for a positive contribution of arsenite and iron oxidizers to arsenic removal upon injection with oxygenated water, but also indicate a potential risk for arsenic re-mobilization by anaerobic arsenate and iron reducers once injection is halted. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Shape control of the magnetic iron oxide nanoparticles under different chain length of reducing agents

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

Ngoi, Kuan Hoon; Chia, Chin-Hua, E-mail: chia@ukm.edu.my; Zakaria, Sarani

2015-09-25

We report on the effect of using reducing agents with different chain-length on the synthesis of iron oxide nanoparticles by thermal decomposition of iron (III) acetylacetonate in 1-octadecene. This modification allows us to control the shape of nanoparticles into spherical and cubic iron oxide nanoparticles. The highly monodisperse 14 nm spherical nanoparticles are obtained under 1,2-dodecanediol and average 14 nm edge-length cubic iron oxide nanoparticles are obtained under 1,2-tetradecanediol. The structural characterization such as transmission electron microscope (TEM) and X-ray diffraction (XRD) shows similar properties between two particles with different shapes. The vibrating sample magnetometer (VSM) shows no significant difference between sphericalmore » and cubic nanoparticles, which are 36 emu/g and 37 emu/g respectively and superparamagnetic in nature.« less

Plasma synthesis, Mössbauer spectroscopy and X-ray diffraction studies of nanosized iron oxides

NASA Astrophysics Data System (ADS)

Paneva, Daniela; Zaharieva, Katerina; Grabis, Janis; Mitov, Ivan; Vissokov, Gheorghi

2010-06-01

In this article synthesis and study of iron oxide nanopowders are described. The synthesis of sample 1 and sample 2—iron oxides—was carried out by electric arc plasma cutting of ordinary steel. The sample 3 was prepared by evaporation of Fe2O3/FeO mixture in radio-frequency nitrogen plasma. The characterization of the as prepared iron oxide nanoproducts was achieved by means of Mössbauer spectroscopy and X-ray diffraction analysis. The presence of different phases of iron oxide with a basic phase Fe3 - xO4 (magnetite), additional Fe1 - xO (wüstite) and α or γ-Fe2O3 (hematite or maghemite) with superparamagnetic particles for sample 1 and sample 2 and Fe3 - xO4 (magnetite) for sample 3 is observed.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Tropical forest soil microbial communities couple iron and carbon biogeochemistry

Treesearch

Eric A. Dubinsky; Whendee L. Silver; Mary K. Firestone

2010-01-01

We report that iron-reducing bacteria are primary mediators of anaerobic carbon oxidation in upland tropical soils spanning a rainfall gradient (3500–5000 mm/yr) in northeast Puerto Rico. The abundant rainfall and high net primary productivity of these tropical forests provide optimal soil habitat for iron-reducing and iron-oxidizing bacteria. Spatially and temporally...

Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

DOEpatents

Rashid Khan, M.

1988-05-05

A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere is described. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis. 4 figs., 8 tabs.

Use of ultrasmall superparamagnetic iron oxide particles for imaging carotid atherosclerosis.

PubMed

Usman, Ammara; Sadat, Umar; Patterson, Andrew J; Tang, Tjun Y; Varty, Kevin; Boyle, Jonathan R; Armon, Mathew P; Hayes, Paul D; Graves, Martin J; Gillard, Jonathan H

2015-10-01

Based on the results of histopathological studies, inflammation within atherosclerotic tissue is now widely accepted as a key determinant of the disease process. Conventional imaging methods can highlight the location and degree of luminal stenosis but not the inflammatory activity of the plaque. Iron oxide-based MRI contrast media particularly ultrasmall supermagnetic particles of iron oxide have shown potential in assessing atheromatous plaque inflammation and in determining efficacy of antiatherosclerosis pharmacological treatments. In this paper, we review current data on the use of ultrasmall superparamagnetic iron oxides in atherosclerosis imaging with focus on ferumoxtran-10 and ferumoxytol. The basic chemistry, pharmacokinetics and dynamics, potential applications, limitations and future perspectives of these contrast media nanoparticles are discussed.

Environment friendly route of iron oxide nanoparticles from Zingiber officinale (ginger) root extract

NASA Astrophysics Data System (ADS)

Xin Hui, Yau; Yi Peng, Teoh; Wei Wen, Liu; Zhong Xian, Ooi; Peck Loo, Kiew

2016-11-01

Iron oxide nanoparticles were prepared from the reaction between the Zingiber officinale (ginger) root extracts and ferric chloride solution at 50°C for 2 h in mild stirring condition. The synthesized powder forms of nanoparticles were further characterized by using UV-Vis spectroscopy and X-ray Diffraction spectrometry. UV-Vis analysis shows the absorption peak of iron oxide nanoparticles is appeared at 370 nm. The calculation of crystallite size from the XRD showed that the average particle size of iron oxide nanoparticles was 68.43 nm. Therefore, this eco-friendly technique is low cost and large scale nanoparticles synthesis to fulfill the demand of various applications.

Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

DOEpatents

Liu, Chain T.

1988-03-15

Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

Preparation and characterization of hydroxyapatite-coated iron oxide particles by spray-drying technique.

PubMed

Donadel, Karina; Felisberto, Marcos D V; Laranjeira, Mauro C M

2009-06-01

Magnetic particles of iron oxide have been increasingly used in medical diagnosis by magnetic resonance imaging and in cancer therapies involving targeted drug delivery and magnetic hyperthermia. In this study we report the preparation and characterization of iron oxide particles coated with bioceramic hydroxyapatite by spray-drying. The iron oxide magnetic particles (IOMP) were coated with hydroxyapatite (HAp) by spray-drying using two IOMP/HAp ratios (0.7 and 3.2). The magnetic particles were characterized by way of scanning electronic microscopy, energy dispersive X-ray, X-ray diffraction, Fourier transformed infrared spectroscopy, flame atomic absorption spectrometry,vibrating sample magnetometry and particle size distribution (laser diffraction). The surface morphology of the coated samples is different from that of the iron oxide due to formation of hydroxyapatite coating. From an EDX analysis, it was verified that the surface of the coated magnetic particles is composed only of HAp, while the interior containsiron oxide and a few layers of HAp as expected. The results showed that spray-drying technique is an efficient and relatively inexpensive method for forming spherical particles with a core/shell structure.

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

A proteome analysis of the response of a Pseudomonas aeruginosa oxyR mutant to iron limitation.

PubMed

Vinckx, Tiffany; Wei, Qing; Matthijs, Sandra; Noben, Jean-Paul; Daniels, Ruth; Cornelis, Pierre

2011-06-01

In Pseudomonas aeruginosa the response to oxidative stress is orchestrated by the LysR regulator OxyR by activation of the transcription of two catalase genes (katA and katB), of the alkyl-hydroxyperoxidases ahpCF and ahpB. Next to the expected high sensitivity to oxidative stress generated by reactive oxygen species (ROS: H(2)O(2), O(2)(-)), the oxyR mutant shows a defective growth under conditions of iron limitation (Vinckx et al. 2008). Although production and uptake of the siderophore pyoverdine is not affected by the absence of oxyR, the mutant is unable to satisfy its need for iron when grown under iron limiting conditions. In order to get a better insight into the effects caused by iron limitation on the physiological response of the oxyR mutant we decided to compare the proteomes of the wild type and the mutant grown in the iron-poor casamino acids medium (CAA), in CAA plus H(2)O(2), and in CAA plus the strong iron chelator ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (EDDHA). Especially in the presence of hydrogen peroxide the oxyR cells increase the production of stress proteins (Dps and IbpA). The superoxide dismutase SodM is produced in higher amounts in the oxyR mutant grown in CAA plus H(2)O(2). The PchB protein, a isochorismate-pyruvate lyase involved in the siderophore pyochelin biosynthesis is not detectable in the extracts from the oxyR mutant grown in the presence of hydrogen peroxide. When cells were grown in the presence of EDDHA, we observed a reduction of the ferric uptake regulator (Fur), and an increase in the two subunits of the succinyl-CoA synthetase and the fumarase FumC1.

Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy. [deuterium-carbon monoxide reaction catalysis

NASA Technical Reports Server (NTRS)

Nooner, D. W.; Gibert, J. M.; Gelpi, E.; Oro, J.

1976-01-01

Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

Influence of moderate pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon.

PubMed

Wang, Zhengfang; Shi, Mo; Li, Jihua; Zheng, Zheng

2014-03-01

A novel adsorbent based on iron oxide dispersed over activated carbon (AC) were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron (denoted as AC-Fe and AC/O-Fe), resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%-46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe(II) after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe(II) by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/O-Fe, respectively. The results showed that the surface mass transfer and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

New Perspectives on Biomedical Applications of Iron Oxide Nanoparticles.

PubMed

Magro, Massimiliano; Baratella, Davide; Bonaiuto, Emanuela; de A Roger, Jessica; Vianello, Fabio

2018-02-12

Iron oxide nanomaterials are considered promising tools for improved therapeutic efficacy and diagnostic applications in biomedicine. Accordingly, engineered iron oxide nanomaterials are increasingly proposed in biomedicine, and the interdisciplinary researches involving physics, chemistry, biology (nanotechnology) and medicine have led to exciting developments in the last decades. The progresses of the development of magnetic nanoparticles with tailored physico-chemical and surface properties produced a variety of clinically relevant applications, spanning from magnetic resonance imaging (MRI), drug delivery, magnetic hyperthermia, to in vitro diagnostics. Notwithstanding the wellknown conventional synthetic procedures and their wide use, along with recent advances in the synthetic methods open the door to new generations of naked iron oxide nanoparticles possessing peculiar surface chemistries, suitable for other competitive biomedical applications. New abilities to rationally manipulate iron oxides and their physical, chemical, and biological properties, allow the emersion of additional possibilities for designing novel nanomaterials for theranostic applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Size distribution of magnetic iron oxide nanoparticles using Warren-Averbach XRD analysis

NASA Astrophysics Data System (ADS)

Mahadevan, S.; Behera, S. P.; Gnanaprakash, G.; Jayakumar, T.; Philip, J.; Rao, B. P. C.

2012-07-01

We use the Fourier transform based Warren-Averbach (WA) analysis to separate the contributions of X-ray diffraction (XRD) profile broadening due to crystallite size and microstrain for magnetic iron oxide nanoparticles. The profile shape of the column length distribution, obtained from WA analysis, is used to analyze the shape of the magnetic iron oxide nanoparticles. From the column length distribution, the crystallite size and its distribution are estimated for these nanoparticles which are compared with size distribution obtained from dynamic light scattering measurements. The crystallite size and size distribution of crystallites obtained from WA analysis are explained based on the experimental parameters employed in preparation of these magnetic iron oxide nanoparticles. The variation of volume weighted diameter (Dv, from WA analysis) with saturation magnetization (Ms) fits well to a core shell model wherein it is known that Ms=Mbulk(1-6g/Dv) with Mbulk as bulk magnetization of iron oxide and g as magnetic shell disorder thickness.

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Synthesis, characterization, applications, and challenges of iron oxide nanoparticles

PubMed Central

Ali, Attarad; Zafar, Hira; Zia, Muhammad; ul Haq, Ihsan; Phull, Abdul Rehman; Ali, Joham Sarfraz; Hussain, Altaf

2016-01-01

Recently, iron oxide nanoparticles (NPs) have attracted much consideration due to their unique properties, such as superparamagnetism, surface-to-volume ratio, greater surface area, and easy separation methodology. Various physical, chemical, and biological methods have been adopted to synthesize magnetic NPs with suitable surface chemistry. This review summarizes the methods for the preparation of iron oxide NPs, size and morphology control, and magnetic properties with recent bioengineering, commercial, and industrial applications. Iron oxides exhibit great potential in the fields of life sciences such as biomedicine, agriculture, and environment. Nontoxic conduct and biocompatible applications of magnetic NPs can be enriched further by special surface coating with organic or inorganic molecules, including surfactants, drugs, proteins, starches, enzymes, antibodies, nucleotides, nonionic detergents, and polyelectrolytes. Magnetic NPs can also be directed to an organ, tissue, or tumor using an external magnetic field for hyperthermic treatment of patients. Keeping in mind the current interest in iron NPs, this review is designed to report recent information from synthesis to characterization, and applications of iron NPs. PMID:27578966

The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?

NASA Astrophysics Data System (ADS)

Balind, K.; Barber, A.; Gélinas, Y.

2017-12-01

The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water.

PubMed

Nieto-Delgado, Cesar; Rangel-Mendez, Jose Rene

2012-06-01

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl(3) concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7. Copyright © 2012 Elsevier Ltd. All rights reserved.

Central roles of iron in the regulation of oxidative stress in the yeast Saccharomyces cerevisiae.

PubMed

Matsuo, Ryo; Mizobuchi, Shogo; Nakashima, Maya; Miki, Kensuke; Ayusawa, Dai; Fujii, Michihiko

2017-10-01

Oxygen is essential for aerobic organisms but causes cytotoxicity probably through the generation of reactive oxygen species (ROS). In this study, we screened for the genes that regulate oxidative stress in the yeast Saccharomyces cerevisiae, and found that expression of CTH2/TIS11 caused an increased resistance to ROS. CTH2 is up-regulated upon iron starvation and functions to remodel metabolism to adapt to iron starvation. We showed here that increased resistance to ROS by CTH2 would likely be caused by the decreased ROS production due to the decreased activity of mitochondrial respiration, which observation is consistent with the fact that CTH2 down-regulates the mitochondrial respiratory proteins. We also found that expression of CTH1, a paralog of CTH2, also caused an increased resistance to ROS. This finding supported the above view, because mitochondrial respiratory proteins are the common targets of CTH1 and CTH2. We further showed that supplementation of iron in medium augmented the growth of S. cerevisiae under oxidative stress, and expression of CTH2 and supplementation of iron collectively enhanced its growth under oxidative stress. Since CTH2 is regulated by iron, these findings suggested that iron played crucial roles in the regulation of oxidative stress in S. cerevisiae.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

PubMed

Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

2015-09-01

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

Depth-dependent geochemical and microbiological gradients in Fe(III) deposits resulting from coal mine-derived acid mine drainage

PubMed Central

Brantner, Justin S.; Haake, Zachary J.; Burwick, John E.; Menge, Christopher M.; Hotchkiss, Shane T.; Senko, John M.

2014-01-01

We evaluated the depth-dependent geochemistry and microbiology of sediments that have developed via the microbially-mediated oxidation of Fe(II) dissolved in acid mine drainage (AMD), giving rise to a 8–10 cm deep “iron mound” that is composed primarily of Fe(III) (hydr)oxide phases. Chemical analyses of iron mound sediments indicated a zone of maximal Fe(III) reducing bacterial activity at a depth of approximately 2.5 cm despite the availability of dissolved O2 at this depth. Subsequently, Fe(II) was depleted at depths within the iron mound sediments that did not contain abundant O2. Evaluations of microbial communities at 1 cm depth intervals within the iron mound sediments using “next generation” nucleic acid sequencing approaches revealed an abundance of phylotypes attributable to acidophilic Fe(II) oxidizing Betaproteobacteria and the chloroplasts of photosynthetic microeukaryotic organisms in the upper 4 cm of the iron mound sediments. While we observed a depth-dependent transition in microbial community structure within the iron mound sediments, phylotypes attributable to Gammaproteobacterial lineages capable of both Fe(II) oxidation and Fe(III) reduction were abundant in sequence libraries (comprising ≥20% of sequences) from all depths. Similarly, abundances of total cells and culturable Fe(II) oxidizing bacteria were uniform throughout the iron mound sediments. Our results indicate that O2 and Fe(III) reduction co-occur in AMD-induced iron mound sediments, but that Fe(II)-oxidizing activity may be sustained in regions of the sediments that are depleted in O2. PMID:24860562

Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

PubMed

Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

2015-11-03

Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

Magnetic Nanoparticle-Based Imaging of RNA Transcripts in Breast Cancer Cells

DTIC Science & Technology

2008-06-30

control (Months 33 – 36). These studies have not yet commenced. KEY RESEARCH ACCOMPLISHMENTS: - Synthesized dextran-coated iron oxide NPs with...Size, charge, and concentration dependent uptake of iron oxide nanoparticles by non-phagocytic cells: a comparative study of USPIO, SSPIO, and MPIO...A. (2008) Size, charge, and concentration dependent uptake of iron oxide nanoparticles by non-phagocytic cells: a comparative study of USPIO, SSPIO