Travel Distance and Transformation of Injected Emulsified Zerovalent Iron Nanoparticles in the Subsurface During Two and Half Years

EPA Science Inventory

Nanoscale zerovalent iron (NZVI) such as Toda Kogyo RNIP-10DS has been used for site remediation, yet information is lacking regarding how far injected NZVI can travel, how long it lasts, and how it transforms to other minerals in a groundwater system. Previously we reported effe...

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Stimulation of Peanut Seedling Development and Growth by Zero-Valent Iron Nanoparticles at Low Concentrations

PubMed Central

Li, Xuan; Yang, Yuechao; Gao, Bin; Zhang, Min

2015-01-01

Because of its strong pollutant degradation ability, nanoscale zerovalent iron (NZVI) has been introduced to soils and groundwater for remediation purposes, but its impacts on plants are still not very clear. In this work, the effects of low concentration (10–320 μmol/L) NZVI particles on seed germination and growth of peanut plants were evaluated. The exposure of peanut seeds to NZVI at all the tested concentrations altered the seed germination activity, especially the development of seedlings. In comparison with the deionized water treated controls (CK), all of the NZVI treatments had significantly larger average lengths. Further investigations with transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) suggested that NZVI particles may penetrate the peanut seed coats to increase the water uptake to stimulate seed germination. The growth experiments showed that although NZVI at a relatively high concentration (320μmol/L) showed phytotoxicity to the peanut plants, the lower concentrations of NZVI particles stimulated the growth and root development of the plants. At certain concentrations (e.g., 40 and 80 μmol/L), the NZVI treated samples were even better than the ethylenediaminetetraacetate-iron (EDTA-Fe) solution, a commonly used iron nutrient solution, in stimulating the plant growth. This positive effect was probably due to the uptake of NZVI by the plants, as indicated in the TEM analyses. Because low concentrations of NZVI particles stimulated both the seedling development and growth of peanut, they might be used to benefit the growth of peanuts in large-scale agricultural settings. PMID:25901959

Removal of hexavalent chromium in soil and groundwater by supported nano zero-valent iron on silica fume.

PubMed

Li, Yongchao; Jin, Zhaohui; Li, Tielong; Li, Shujing

2011-01-01

Silica fume supported-Fe(0) nanoparticles (SF-Fe(0)) were prepared using commercial silica fume as a support. The feasibility of using this SF-Fe(0) for reductive immobilization of Cr(VI) was investigated through batch tests. Compared with unsupported Fe(0), SF-Fe(0) was significantly more active in Cr(VI) removal especially in 84 wt% silica fume loading. Silica fume had also been found to inhibit the formation of Fe(III)/Cr(III) precipitation on Fe nanoparticles' surface, which was increasing the deactivation resistance of iron. Cr(VI) was removed through physical adsorption of Cr(VI) onto the SF-Fe(0) surface and subsequent reduction of Cr(VI) to Cr(III). The rate of reduction of Cr(VI) could be expressed by pseudo first-order reaction kinetics. The rate constant increased with the increase in iron loading but decreased with the increase in initial Cr(VI) concentration. Furthermore, column tests showed that the SF-Fe(0) could be readily transported in model soil.

Novel sequential process for enhanced dye synergistic degradation based on nano zero-valent iron and potassium permanganate.

PubMed

Wang, Xiangyu; Liu, Peng; Fu, Minglai; Ma, Jun; Ning, Ping

2016-07-01

A novel synergistic technology based on nano zero-valent iron (NZVI) and potassium permanganate (KMnO4) was developed for treatment of dye wastewater. The synergistic technology was significantly superior, where above 99% of methylene blue (MB) was removed, comparatively, removal efficiencies of MB with the sole technology of NZVI and KMnO4 at pH 6.39 being 52.9% and 63.1%, respectively. The advantages of this technology include (1) the in situ formed materials (manganese (hydr)oxides, iron hydroxides and MnFe oxide), resulting in the stable and high removal efficiency of MB and (2) high removal capacity in a wide range of pH value. Compared with simultaneous addition system of NZVI and KMnO4, MB removal was remarkably improved by sequential addition system, especially when KMnO4 addition time was optimized at 20 min. Analyses of crystal structure (XRD), morphological difference (FE-SEM), element valence and chemical groups (XPS) of NZVI before and after reaction had confirmed the formation of in situ materials, which obviously enhanced removal of MB by oxidation and adsorption. More importantly, the roles of in situ formed materials and degradation mechanism were innovatively investigated, and the results suggested that NCH3 bond of MB molecule was attacked by oxidants (KMnO4 and in situ manganese (hydr)oxides) at position C1 and C9, resulting in cleavage of chromophore. This study provides new insights about an applicable technology for treatment of dye wastewater. Copyright © 2016. Published by Elsevier Ltd.

KINETICS OF TRICHLOROETHENE REDUCTION BY ZEROVALENT IRON AND TIN: PRETREATMENT EFFECT, APPARENT ACTIVATION ENERGY, AND INTERMEDIATE PRODUCTS

EPA Science Inventory

The degradation of trichloroethene (TCE) at 2 mg L-1 in headspace free aqueous solution by zerovalent iron (Feo) and tin (Sno) was studied in batch tests at 10, 25, 40, and 55 degrees C and HCI-treated Feo and Sno at 25 and 55 degrees C. The HCI-washing increased metal surface a...

KINETICS OF SOLUBLE CHROMIUM REMOVAL FROM CONTAMINATED WATER BY ZEROVALENT IRON MEDIA: CORROSION INHIBITION AND PASSIVE OXIDE EFFECTS. (R825223)

EPA Science Inventory

Permeable reactive barriers containing zerovalent iron are being increasingly
employed for in situ remediation of groundwater contaminated with redox active
metals and chlorinated organic compounds. This research investigated the effect
of chromate concentration on...

[Enhanced remediation of 4-chloronitrobenzene contaminated groundwater with nanoscale zero-valence iron (nZVI) catalyzed hydrogen peroxide (H2O2)].

PubMed

Fu, Rong-Bing

2014-04-01

Chemical oxidation-reduction technology is an important way to quickly remedy contaminated groundwater. Nanoscale zero-valent iron (nZVI) was produced by liquid-phase reduction using FeSO4 and NaBH4, and characterized by SEM and XRD. The remediation of 4-chloronitrobezene (4-CINB) contaminated groundwater at ambient temperature and pressure was conducted with the nZVI catalytic H2O2 process, and the affecting factors and degradation mechanisms were investigated. The results indicated that under initial pH 3.0 at the temperature of 30 degrees C, after 30 mins of reaction, 4-ClNB in groundwater was completely degraded when the concentrations of nZVI and H2O2 were 268.8 mg x L(-1) and 4.90 mmol x L(-1), respectively. 4-chloronitrosobenzene, 4-chlorophenylhydroxylamine, 4-chloroazoxybenzene, 4-chloroaniline, 4-chloroazobenzene, 4-benzoquinone, acetic acid, formic acid, oxalic acid and chlorine ion were identified as the major intermediates of 4-ClNB degradation after the process. A tentative pathway for the degradation of 4-ClNB was proposed.

A method for determination of [Fe3+]/[Fe2+] ratio in superparamagnetic iron oxide

NASA Astrophysics Data System (ADS)

Jiang, Changzhao; Yang, Siyu; Gan, Neng; Pan, Hongchun; Liu, Hong

2017-10-01

Superparamagnetic iron oxide nanoparticles (SPION), as a kind of nanophase materials, are widely used in biomedical application, such as magnetic resonance imaging (MRI), drug delivery, and magnetic field assisted therapy. The magnetic property of SPION has close connection with its crystal structure, namely it is related to the ratio of Fe3+ and Fe2+ which form the SPION. So a simple way to determine the content of the Fe3+ and Fe2+ is important for researching the property of SPION. This review covers a method for determination of the Fe3+ and Fe2+ ratio in SPION by UV-vis spectrophotometry based the reaction of Fe2+ and 1,10-phenanthroline. The standard curve of Fe with R2 = 0.9999 is used for determination the content of Fe2+ and total iron with 2.5 mL 0.01% (w/v) SPION digested by HCl, pH = 4.30 HOAc-NaAc buffer 10 mL, 0.01% (w/v) 1,10-phenanthroline 5 mL and 10% (w/v) ascorbic acid 1 mL for total iron determine independently. But the presence of Fe3+ interfere with obtaining the actual value of Fe2+ (the error close to 9%). We designed a calibration curve to eliminate the error by devising a series of solution of different ratio of [Fe3+]/[Fe2+], and obtain the calibration curve. Through the calibration curve, the error between the measured value and the actual value can be reduced to 0.4%. The R2 of linearity of the method is 0.99441 and 0.99929 for Fe2+ and total iron respectively. The error of accuracy of recovery and precision of inter-day and intra-day are both lower than 2%, which can prove the reliability of the determination method.

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

PubMed

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

2016-03-01

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

Hydraulic and geochemical performance of a permeable reactive barrier containing zero-valent iron, Denver Federal Center

USGS Publications Warehouse

McMahon, P.B.; Dennehy, K.F.; Sandstrom, M.W.

1999-01-01

The hydraulic and geochemical performance of a 366 m long permeable reactive barrier (PRB) at the Denver Federal Center; Denver, Colorado, was evaluated. The funnel and gate system, which was installed in 1996 to intercept and remediate ground water contaminated with chlorinated aliphatic hydrocarbons (CAHs), contained four 12.2 m wide gates filled with zero-valent iron. Ground water mounding on the upgradient side of the PRB resulted in a tenfold increase in the hydraulic gradient and ground water velocity through the gates compared to areas of the aquifer unaffected by the PRB. Water balance calculations for April 1997 indicate that about 75% of the ground water moving toward the PRB from upgradient areas moved through the gates. The rest of the water either accumulated on the upgradient side of the PRB or bypassed the PRB. Chemical data from monitoring wells screened down-gradient, beneath, and at the ends of the PRB indicate that contaminants had not bypassed the PRB, except in a few isolated areas. Greater than 99% of the CAH mass entering the gates was retained by the iron. Fifty-one percent of the CAH carbon entering one gate was accounted for in dissolved C1 and C2 hydrocarbons, primarily ethane and ethene, which indicates that CAHs may adsorb to the iron prior to being dehalogenated. Treated water exiting the gates displaced contaminated ground water at a distance of at least 3 m downgradient from the PRB by the end of 1997. Measurements of dissolved inorganic ions in one gate indicate that calcite and siderite precipitation in the gate could reduce gate porosity by about 0.35% per year. Results from this study indicate that funnel and gate systems containing zero-valent iron can effectively treat ground water contaminated with CAHs. However, the hydrologic impacts of the PRB on the flow system need to be fully understood to prevent contaminants from bypassing the PRB.

Preparation and characterization of bismuth oxichloride (BiOCl) nanoparticles and nano zerovalent iron (nZVI)

NASA Astrophysics Data System (ADS)

Sarwan, Bhawna; Pare, Brijesh; Deep Acharya, Aman

2017-05-01

In this work, we have synthesized nano scale zerovalent iron (nZVI) particles by borohydride reduction method and bismuth oxichloride (BiOCl) by a hydrolysis method. X-ray powder diffraction (XRD) was used for the structural and chemical characterization, while scanning/transmission electron microscopy (SEM/TEM) were employed to determine the physical properties of the nanoparticles. The reactivity of synthesized nanoparticles was compared by decolorization of nile blue (NB) dye under visible irradiation.

Pressure-induced phase transitions and correlation between structure and superconductivity in iron-based superconductor Ce(O(0.84)F(0.16))FeAs.

PubMed

Zhao, Jinggeng; Liu, Haozhe; Ehm, Lars; Dong, Dawei; Chen, Zhiqiang; Liu, Qingqing; Hu, Wanzheng; Wang, Nanlin; Jin, Changqing

2013-07-15

High-pressure angle-dispersive X-ray diffraction experiments on iron-based superconductor Ce(O(0.84)F(0.16))FeAs were performed up to 54.9 GPa at room temperature. A tetragonal to tetragonal isostructural phase transition starts at about 13.9 GPa, and a new high-pressure phase has been found above 33.8 GPa. At pressures above 19.9 GPa, Ce(O(0.84)F(0.16))FeAs completely transforms to a high-pressure tetragonal phase, which remains in the same tetragonal structure with a larger a-axis and smaller c-axis than those of the low-pressure tetragonal phase. The structure analysis shows a discontinuity in the pressure dependences of the Fe-As and Ce-(O, F) bond distances, as well as the As-Fe-As and Ce-(O, F)-Ce bond angles in the transition region, which correlates with the change in T(c) of this compound upon compression. The isostructural phase transition in Ce(O(0.84)F(0.16))FeAs leads to a drastic drop in the superconducting transition temperature T(c) and restricts the superconductivity at low temperature. For the 1111-type iron-based superconductors, the structure evolution and following superconductivity changes under compression are related to the radius of lanthanide cations in the charge reservoir layer.

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

PubMed

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

2014-10-01

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

Continuous preparation of nanoscale zero-valent iron using impinging stream-rotating packed bed reactor and their application in reduction of nitrobenzene

NASA Astrophysics Data System (ADS)

Jiao, Weizhou; Qin, Yuejiao; Luo, Shuai; Feng, Zhirong; Liu, Youzhi

2017-02-01

Nanoscale zero-valent iron (nZVI) was continuously prepared by high-gravity reaction precipitation through a novel impinging stream-rotating packed bed (IS-RPB). Reactant solutions of FeSO4 and NaBH4 were conducted into the IS-RPB with flow rates of 60 L/h and rotating speed of 1000 r/min for the preparation of nZVI. As-prepared nZVI obtained by IS-RPB were quasi-spherical morphology and almost uniformly distributed with a particle size of 10-20 nm. The reactivity of nZVI was estimated by the degradation of 100 ml nitrobenzene (NB) with initial concentration of 250 mg/L. The optimum dosage of nZVI obtained by IS-RPB was 4.0 g/L as the NB could be completely removed within 10 min, which reduced 20% compared with nZVI obtained by stirred tank reactor (STR). The reduction of NB and production of aniline (AN) followed pseudo-first-order kinetics, and the pseudo-first-order rate constants were 0.0147 and 0.0034 s-1, respectively. Furthermore, the as-prepared nZVI using IS-RPB reactor in this work can be used within a relatively wide range pH of 1-9.

Facile green synthesis of functional nanoscale zero-valent iron and studies of its activity toward ultrasound-enhanced decolorization of cationic dyes.

PubMed

Wang, Xiangyu; Wang, Anqi; Ma, Jun; Fu, Minglai

2017-01-01

For the first time, an integrated green technology by coupling functional nanoscale zero-valent iron (NZVI) with ultrasound (US) was innovatively developed for the enhanced decolorization of malachite green (MG) and methylene blue (MB). The functional NZVI (TP-Fe) was successfully fabricated via a facile, one-step and environmentally-benign approach by directly introducing high pure tea polyphenol (TP), where TP contenting abundant epicatechin was employed as reductant, dispersant and capping agent. Note that neither additional extraction procedure nor protection gas was needed during the entire synthesis process. Affecting factors (including US frequency, initial pH, dye concentration, and reaction temperature) were investigated. Results show that TP-Fe exhibited enhanced activity, antioxidizability and stability over the reaction course, which could be attributed to the functionalization of TP on NZVI and the invigorating effect of US (i.e., improving the mass transfer rate, breaking up the aggregates of TP-Fe nanoparticles, and maintaining the TP-Fe surface activity). The kinetics for MG and MB decolorization by the TP-Fe/US system could be well described by a two-parameter pseudo-first-order decay model, and the activation energies of MG and MB decolorization in this new system were determined to be 21 kJ mol -1 and 24 kJ mol -1 , respectively. In addition, according to the identified reaction products, a possible mechanism associated with MG and MB decolorization with the TP-Fe/US system was proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed Central

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-01-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions. PMID:26355955

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co(2+) Solution: Interactional Performance and Mechanism.

PubMed

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-10

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co(2+) solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co(2+) reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the "structural influence" crucial for the full and dynamical understanding of nZVI reactions.

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

NASA Astrophysics Data System (ADS)

Zhang, Yalei; Chen, Wen; Dai, Chaomeng; Zhou, Chuanlong; Zhou, Xuefei

2015-09-01

The structures of nanoscale zero-valent iron (nZVI) particles evolving during reactions, and the reactions are influenced by the evolved structures. To understand the removal process in detail, it is important to investigate the relationships between the reactions and structural evolution. Using high resolution-transmission electron microscopy (HR-TEM), typical evolved structures (sheet coprecipitation and cavity corrosion) of nZVI in anoxic Co2+ solutions were revealed. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the nZVI corrosion rate, were found to be the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results indicated that the formation and dissolution of sheet structure impacts on the ratio of Fe(0) on the nZVI surface and the surface Co2+ reduction. The cavity structure provides the possibility of Co migration from the surface to the bulk of nZVI, leading to continuous removal. Subacidity conditions could accelerate the evolution and improve the removal; the results of structurally controlled reactions further indicated that the removal was suspended by the sheet structure and enhanced by cavity structure. The results and discussion in this paper revealed the “structural influence” crucial for the full and dynamical understanding of nZVI reactions.

Static compression of Fe 0.83Ni 0.09Si 0.08 alloy to 374 GPa and Fe 0.93Si 0.07 alloy to 252 GPa: Implications for the Earth's inner core

NASA Astrophysics Data System (ADS)

Asanuma, Hidetoshi; Ohtani, Eiji; Sakai, Takeshi; Terasaki, Hidenori; Kamada, Seiji; Hirao, Naohisa; Ohishi, Yasuo

2011-10-01

The pressure-volume equations of state of iron-nickel-silicon alloy Fe 0.83Ni 0.09Si 0.08 (Fe-9.8 wt.% Ni-4.0 wt.% Si) and iron-silicon alloy Fe 0.93Si 0.07 (Fe-3.4 wt.% Si) have been investigated up to 374 GPa and 252 GPa, respectively. The present compression data covered pressures of the Earth's core. We confirmed that both Fe 0.83Ni 0.09Si 0.08 and Fe 0.93Si 0.07 alloys remain in the hexagonal close packed structure at all pressures studied. We obtained the density of these alloys at the pressure of the inner core boundary (ICB), 330 GPa at 300 K by fitting the compression data to the third order Birch-Murnaghan equation of state. Using these density values combined with the previous data for hcp-Fe, hcp-Fe 0.8Ni 0.2, and hcp-Fe 0.84Si 0.16 alloys and comparing with the density of the PREM inner core, we estimated the Ni and Si contents of the inner core. The Si content of the inner core estimated here is slightly greater than that estimated previously based on the sound velocity measurement of the hcp-Fe-Ni-Si alloy at high pressure.

Reducing the mobility of arsenic in brownfield soil using stabilised zero-valent iron nanoparticles.

PubMed

Gil-Díaz, Mar; Alonso, Juan; Rodríguez-Valdés, Eduardo; Pinilla, Paloma; Lobo, Maria Carmen

2014-01-01

The use of nanoscale zero-valent iron (nZVI) as a new tool for the treatment of polluted soils and groundwater has received considerable attention in recent years due to its high reactivity, in situ application and cost-effectiveness. The objectives of this study were to investigate the effectiveness of using a commercial stabilised suspension of nZVI to immobilise As in brownfield soil and to investigate its impact on Fe availability in the treated soil. The phytotoxicities of the soil samples were also evaluated using a germination test with two plant species: barley (Hordeum vulgare L) and common vetch (Vicia sativa L). Two doses of the commercial nZVI suspension were studied, 1% and 10%, and two soil-nanoparticle interaction times, 72 h and 3 mo, were used to compare the stabilities of the soils treated with nZVI. The As availability was evaluated using a sequential extraction procedure and the toxicity characteristics leaching procedure (TCLP) test. The application of nZVI significantly decreased the availability of As in the soil. The immobilisation of As was more effective and more stable over time with the 10% dose than with the 1% dose of the commercial nZVI suspension. The application of nZVI did not induce an important increase in Fe mobility because the Fe leachability was less than 2 mg L(-1) over the time period studied. The lower availability of As in the soil led to a decrease in the phytotoxicity of the soil to barley and vetch germination. Thus, the proposed nanotechnology could be a potential alternative for the in situ remediation of As-polluted soils and could be combined with remediation processes where plants are involved.

Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

EPA Science Inventory

A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...

Use of agar agar stabilized milled zero-valent iron particles for in situ groundwater remediation

NASA Astrophysics Data System (ADS)

Schmid, Doris; Velimirović, Milica; Wagner, Stephan; Micić Batka, Vesna; von der Kammer, Frank; Hofmann, Thilo

2015-04-01

A major obstacle for use of nanoscale zero-valent iron (nZVI) particles as a nontoxic material for effective in situ degradation of chlorinated aliphatic hydrocarbons (CAHs) is the high production cost. For that reason, submicro-scale milled zero-valent iron particles were recently developed (milled ZVI, UVR-FIA, Germany) by grinding macroscopic raw materials of elementary iron as a cheaper alternative to products produced by solid-state reduction. However, milled ZVI particles tend to aggregate and due to the rather large particle size (d50= 11.9 µm) also rapidly sediment. To prevent aggregation and consequently sedimentation of milled ZVI particles and therefore improve the mobility after in situ application, the use of a stabilizer is considered in literature as a most promising option. In this study, milled ZVI particles (1 g L-1 of particle concentration) were stabilized by environmentally friendly polymer agar agar (>0.5 g L-1), which had a positive impact on the milled ZVI stability. Sedimentation rate was significantly decreased by increasing the suspension viscosity. Column transport experiments were performed for bare and agar agar stabilized milled ZVI particles in commercially available fine grained quartz sand (DORSILIT® Nr.8, Gebrüder Dorfner GmbH Co, Germany) and different porous media collected from brownfields. The experiments were carried out under field relevant injection conditions of 100 m d-1. The maximal travel distance (LT) of less than 10 cm was determined for non-stabilized suspension in fine grained quartz sand, while agar agar (1 g L-1) stabilized milled ZVI suspension revealed LT of 12 m. Similar results were observed for porous media from brownfields showing that mobility of agar agar stabilized particle suspensions was significantly improved compared to bare particles. Based on the mobility data, agar agar stabilized milled zero-valent iron particles could be used for in situ application. Finally, lab-scale batch degradation

Effect of injection velocity and particle concentration on transport of nanoscale zero-valent iron and hydraulic conductivity in saturated porous media

NASA Astrophysics Data System (ADS)

Strutz, Tessa J.; Hornbruch, Götz; Dahmke, Andreas; Köber, Ralf

2016-08-01

Successful groundwater remediation by injecting nanoscale zero-valent iron (NZVI) particles requires efficient particle transportation and distribution in the subsurface. This study focused on the influence of injection velocity and particle concentration on the spatial NZVI particle distribution, the deposition processes and on quantifying the induced decrease in hydraulic conductivity (K) as a result of particle retention by lab tests and numerical simulations. Horizontal column tests of 2 m length were performed with initial Darcy injection velocities (q0) of 0.5, 1.5, and 4.1 m/h and elemental iron input concentrations (Fe0in) of 0.6, 10, and 17 g/L. Concentrations of Fe0 in the sand were determined by magnetic susceptibility scans, which provide detailed Fe0 distribution profiles along the column. NZVI particles were transported farther at higher injection velocity and higher input concentrations. K decreased by one order of magnitude during injection in all experiments, with a stronger decrease after reaching Fe0 concentrations of about 14-18 g/kg(sand). To simulate the observed nanoparticle transport behavior the existing finite-element code OGS has been successfully extended and parameterized for the investigated experiments using blocking, ripening, and straining as governing deposition processes. Considering parameter relationships deduced from single simulations for each experiment (e.g. deposition rate constants as a function of flow velocity) one mean parameter set has been generated reproducing the observations in an adequate way for most cases of the investigated realistic injection conditions. An assessment of the deposition processes related to clogging effects showed that the percentage of retention due to straining and ripening increased during experimental run time resulting in an ongoing reduction of K. Clogging is mainly evoked by straining which dominates particle deposition at higher flow velocities, while blocking and ripening play a

Mechanism, synthesis and modification of nano zerovalent iron in water treatment

NASA Astrophysics Data System (ADS)

Lu, Hai-Jiao; Wang, Jing-Kang; Ferguson, Steven; Wang, Ting; Bao, Ying; Hao, Hong-Xun

2016-05-01

Owing to its strong reducing ability, high reaction activity, excellent adsorption properties, good mobility and relatively low cost, nano zerovalent iron (nZVI) is an extremely promising nanomaterial for use in water treatment. In this paper, the working mechanisms of nZVI in the degradation of various contaminants in water are outlined and discussed. Synthesis methods and their respective advantages and disadvantages are discussed in detail. Furthermore, a variety of modification methods which have been developed to improve the mobility and stability of nZVI as well as to facilitate the separation of nZVI from degraded systems are also summarized and discussed. Numerous studies indicate that nZVI has considerable potential to become an efficient, versatile and practical approach for large-scale water treatment.

Mineral Precipitation Upgradient from a Zero-Valent Iron Permeable Reactive Barrier

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

Johnson, R. L.; Thoms, R. B.; Johnson, R. O.

2008-07-01

Core samples taken from a zero-valent iron permeable reactive barrier (ZVI PRB) at Cornhusker Army Ammunition Plant, Nebraska, were analyzed for physical and chemical characteristics. Precipitates containing iron and sulfide were present at much higher concentrations in native aquifer materials just upgradient of the PRB than in the PRB itself. Sulfur mass balance on core solids coupled with trends in ground water sulfate concentrations indicates that the average ground water flow after 20 months of PRB operation was approximately twenty fold less than the regional ground water velocity. Transport and reaction modeling of the aquifer PRB interface suggests that, atmore » the calculated velocity, both iron and hydrogen could diffuse upgradient against ground water flow and thereby contribute to precipitation in the native aquifer materials. The initial hydraulic conductivity (K) of the native materials is less than that of the PRB and, given the observed precipitation in the upgradient native materials, it is likely that K reduction occurred upgradient to rather than within the PRB. Although not directly implicated, guar gum used during installation of the PRB is believed to have played a role in the precipitation and flow reduction processes by enhancing microbial activity.« less

[Preparation of nano zero-valent iron/Sargassum horneri based activated carbon for removal of Cr (VI) from aqueous solution].

PubMed

Zeng, Gan-Ning; Wu, Xiao; Zheng, Lin; Wu, Xi; Tu, Mei-Ling; Wang, Tie-Gan; Ai, Ning

2015-02-01

Nanoscale zero-valent iron supported on Sargassum horneri activated carbon (NZVI/SAC) was synthesized by zinc chloride activation and incipient wetness method, and characterized with X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). XRD confirmed the existence of nano zero-valent iron, and SEM revealed that the material consisted of mainly 30-150 nm spherical particles aggregated into chains of individual units. The valence state of iron conformed with the nuclear-shell model. The effects of NZVI loading on AC, pH and the initial concentration of Cr(VI) on the removal of Cr(VI) were investigated. The final Cr(VI) removal percentage was up to 100% under the following conditions: 30 degrees C, pH = 2, NZVI/SAC dosage of 2 g x L(-1) and the amounts of NZVI loaded on SAC of 30%. And the equilibrium time was 10 minutes. These results showed that NZVI/SAC could be potentially applied for removal of high concentration Cr(VI). By analyzing the chemical change of NZVI/ SAC, we demonstrated that Cr(VI) was mainly reduced to insoluble Cr (III) compound in the reaction when pH was less than 4, and adsorbed by NZVI and SAC when pH was over 4.

Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

EPA Science Inventory

Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

DDT degradation efficiency and ecotoxicological effects of two types of nano-sized zero-valent iron (nZVI) in water and soil.

PubMed

El-Temsah, Yehia S; Sevcu, Alena; Bobcikova, Katerina; Cernik, Miroslav; Joner, Erik J

2016-02-01

Nano-scale zero-valent iron (nZVI) has been conceived for cost-efficient degradation of chlorinated pollutants in soil as an alternative to e.g permeable reactive barriers or excavation. Little is however known about its efficiency in degradation of the ubiquitous environmental pollutant DDT and its secondary effects on organisms. Here, two types of nZVI (type B made using precipitation with borohydride, and type T produced by gas phase reduction of iron oxides under H2) were compared for efficiency in degradation of DDT in water and in a historically (>45 years) contaminated soil (24 mg kg(-1) DDT). Further, the ecotoxicity of soil and water was tested on plants (barley and flax), earthworms (Eisenia fetida), ostracods (Heterocypris incongruens), and bacteria (Escherichia coli). Both types of nZVI effectively degraded DDT in water, but showed lower degradation of aged DDT in soil. Both types of nZVI had negative impact on the tested organisms, with nZVI-T giving least adverse effects. Negative effects were mostly due to oxidation of nZVI, resulting in O2 consumption and excess Fe(II) in water and soil. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Implementation of zero-valent iron (ZVI) into drinking water supply - role of the ZVI and biological processes.

PubMed

Kowalski, Krzysztof P; Søgaard, Erik G

2014-12-01

Arsenic in drinking water is concerning millions of people around the world, even though many solutions to the problem have come up in recent years. One of the promising solutions for removing arsenic from water is by implementation of a zero-valent iron (ZVI) in the drinking water production. The purpose of this work was to study a treatment of As pollution based on the ZVI, aeration and sand filtration that was monitored for period of 45 months. In applied configuration and conditions ZVI was not able to remove arsenic alone, but it worked as a source of ferrous ions that during its oxidation enabled to co-precipitate arsenic compounds in the sand filter. The results show that after a lag phase of about 6 months, it was possible to achieve water production with an As content from 20 μg L(-1) to below 5 μg L(-1). The treatment also enabled to remove phosphates that were present in groundwater and affected As uptake by hindering its co-precipitation with Fe compounds. Determination of colony forming units on As amended agar helped to find arsenic resistant bacteria at each stage of treatment and also in the sand filter backwash sludge. Bacterial communities found in groundwater, containing low concentration of As, were found to have high As resistance. The results also indicate that the lag phase might have been also needed to initiate Fe ions release by corrosion from elemental Fe by help of microbial activity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

PubMed

Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen

2013-11-01

Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. Copyright © 2013 Elsevier Ltd. All rights reserved.

A combined process of adsorption and Fenton-like oxidation for furfural removal using zero-valent iron residue.

PubMed

Li, Furong; Bao, Jianguo; Zhang, Tian C; Lei, Yutian

2015-01-01

In this study, the feasibility of using a combined adsorption and Fenton-like oxidation process (with zero-valent iron (ZVI) residue from heat wraps as an absorbent and catalyst) to remove furfural in the solution was evaluated. The influencing parameters (e.g. pH, H2O2 concentration, initial furfural concentration) and the reusability of ZVI residue (to replace the iron powder) were estimated. The ZVI residue was found to have much better adsorption effect on furfural at pH 2.0 compared with pH 6.7. For Fenton-like reaction alone with ZVI residue, the highest furfural removal of 97.5% was observed at the concentration of 0.176 mol/L H2O2, and all of the samples had >80% removal efficiency at different initial furfural concentrations of 2, 10, 20, 30 and 40 mmol/L. However, with a combined adsorption and Fenton-like oxidation, the removal efficiency of furfural was nearly 100% for all treatments. The ZVI residue used for furfural removal was much better than that of iron powder in the Fenton-like reaction at a seven-cycle experiment. This study suggests the combined process of adsorption and Fenton-like oxidation using ZVI residue is effective for the treatment of furfural in the liquid.

Improving dewaterability of waste activated sludge by combined conditioning with zero-valent iron and hydrogen peroxide.

PubMed

Zhou, Xu; Wang, Qilin; Jiang, Guangming; Zhang, Xiwang; Yuan, Zhiguo

2014-12-01

Improvement of sludge dewaterability is crucial for reducing the costs of sludge disposal in wastewater treatment plants. This study presents a novel method based on combined conditioning with zero-valent iron (ZVI) and hydrogen peroxide (HP) at pH 2.0 to improve dewaterability of a full-scale waste activated sludge (WAS). The combination of ZVI (0-750mg/L) and HP (0-750mg/L) at pH 2.0 substantially improved the WAS dewaterability due to Fenton-like reactions. The highest improvement in WAS dewaterability was attained at 500mg ZVI/L and 250mg HP/L, when the capillary suction time of the WAS was reduced by approximately 50%. Particle size distribution indicated that the sludge flocs were decomposed after conditioning. Economic analysis showed that combined conditioning with ZVI and HP was a more economically favorable method for improving WAS dewaterability than the classical Fenton reaction based method initiated by ferrous salts and HP. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dechlorination Kinetics Of Monochlorobiphenyls By Fe/Pd: Effects Of Solvent, Temperature, And PCB Concentration

EPA Science Inventory

Well-known, yet undefined, changes in the conditions and activity of palladized zerovalent iron (Fe/Pd) over an extended period of time hindered a careful study of dechlorination kinetics in long-term experiments. A short-term experimental method was, therefore, developed to stud...

Unraveling the catalyzing behaviors of different iron species (Fe2+ vs. Fe0) in activating persulfate-based oxidation process with implications to waste activated sludge dewaterability.

PubMed

Zhen, Guangyin; Lu, Xueqin; Su, Lianghu; Kobayashi, Takuro; Kumar, Gopalakrishnan; Zhou, Tao; Xu, Kaiqin; Li, Yu-You; Zhu, Xuefeng; Zhao, Youcai

2018-05-01

Dewatering of waste activated sludge (WAS) is of major interest in its volume reduction, transportation and ultimate disposal. Persulfate-based oxidation process is a newly developed option for enhancing WAS dewaterability through the generation of powerful sulfate radicals (SO 4 - ·). However, the enhancement in WAS dewaterability by persulfate differs with the species of iron catalysts used. In this study, two types of iron catalysts (i.e. Fe 2+ vs. Fe 0 ) were employed to initiate the persulfate (S 2 O 8 2- ), and the catalyzing behaviors and the underlying principles in enhancing WAS dewaterability were investigated and compared. The Fe 2+ exhibited the high effectiveness in catalyzing the decomposition of persulfate to sulfate radicals (SO 4 - ·), inducing the greater improvement in WAS dewatering. The WAS dewaterability (indicated by dry solids content after filtration) increased with the added S 2 O 8 2- /Fe 2+ dosages, with the dry solids content reaching up to 5.1 ± 0.8 wt% at S 2 O 8 2- /Fe 2+ dosages of 1.2/1.5 mmol/g-VS after only 30 s' filtration, roughly 1.8-fold increase than raw WAS (1.8 ± 0.1 wt%). In contrast, the influence of the persulfate oxidation when activated with Fe 0 on WAS dewaterability was statistically insignificant. The WAS dewaterability remained nearly unchanged (i.e. dry solids content of 2.0 ± 0.0 wt%), irrespective of the employed S 2 O 8 2- /Fe 0 dosages. Further analysis demonstrated that the WAS dewaterability negatively corresponded to loosely bound extracellular polymeric substances (LB-EPS) and tightly bound EPS (TB-EPS). The abundant SO 4 - · from S 2 O 8 2- /Fe 2+ system could effectively disrupt the gel-like EPS matrix, break apart the cells and subsequently arouse the release of the water inside EPS and cells, facilitating water-solid separation. In the case of S 2 O 8 2- /Fe 0 , the dissolution of Fe 0 particles was the rate-limiting step, due to the formation of oxide iron layer near Fe 0

Assessment of the transport of polyvinylpyrrolidone-stabilised zero-valent iron nanoparticles in a silica sand medium

NASA Astrophysics Data System (ADS)

Liang, Bin; Xie, Yingying; Fang, Zhanqiang; Tsang, Eric Pokeung

2014-07-01

Nano zero-valent iron has been considered a promising material for in situ remediation, but its strong tendency to form aggregates makes it difficult to transport in porous media. Thus, stabilization techniques are required to overcome this limitation. In this study, we use polyvinylpyrrolidone (PVP) to synthesise to stabilise iron nanoparticles. The effects of various factors such as nZVI influent concentrations, flow velocity, Ca2+, Mg2+ and humic acid on the transport behaviour of the PVP-nZVI particles were considered. A sedimentation test indicated that PVP-nZVI particles with diameters ranging from 50 to 80 nm were more stable than Bare-nZVI particles. Column experiments demonstrated that PVP-nZVI also exhibited better mobility in silica sand than Bare-nZVI. Due to either the straining or blocking effect, the effluent relative concentration ( C/ C 0) plateau increased with increasing particle concentration. Increasing the flow velocity increased the C/ C 0, resulting in the reduction of overall single-collector contact efficiency ( η 0). Humic acid (HA) enhanced the mobility of PVP-nZVI, and the sedimentation test in the presence of HA suggested that decreased attachment of PVP-nZVI to the silica sand surface rather than decreased aggregation was the primary mechanism of this enhanced mobility.

Synthesis and characterization of Acacia gum-Fe0Np-silica nanocomposite: an efficient Fenton-like catalyst for the degradation of Remazol Brilliant Violet dye

NASA Astrophysics Data System (ADS)

Singh, Vandana; Singh, Jadveer; Srivastava, Preeti

2018-04-01

Acacia gum-Fe0Np-silica nanocomposite (GFS1) has been crafted through sol-gel technique using a two-step process that involved the reduction of iron salt to zerovalent iron nanoparticles (Fe0Nps) followed by their impregnation within Acacia gum-silica matrix. GFS1 was characterized using Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray analysis (EDX), field emission scanning electron microscopy (FE-SEM), vibrating sample magnetometry (VSM), and X-ray photoelectron spectroscopy (XPS) techniques. GFS1 is decorated with Fe0Nps of 5 nm average size. The VSM study revealed that GFS1 has ferromagnetic nature. GFS1 was used as a heterogeneous Fenton-like catalyst for the degradation of azo dyes using Remazol Brilliant Violet (RBV) dye as a model dye. In first 5 min of operation, > 86% dye degradation was achieved and 94% dye (from 100 mg L-1 dye solution) was successfully degraded in 50 min. The dye degradation followed pseudo-first-order kinetics. The GFS1 performed efficiently well over the wide range of dye concentrations (25-200 mg L-1). The catalyst was reused for eight repeated cycles where 12.5% dye degradation was possible even in the eighth cycle. The catalyst behaved fairly well for the degradation of Metanil Yellow (MY) and Orange G (OG) dyes also. Under the optimum conditions of RBV dye degradation, Metanil Yellow (MY) and Orange G (OG) dyes were degraded to the extent of 97 and 26.3%, respectively.

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

USGS Publications Warehouse

Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

2006-01-01

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments

The activated iron system for phosphorus recovery in aqueous environments.

PubMed

Wan, Jun; Jiang, Xiaoqing; Zhang, Tian C; Hu, Jiong; Richter-Egger, Dana; Feng, Xiaonan; Zhou, Aijiao; Tao, Tao

2018-04-01

Finding a good sorbent for phosphorus (P) recovery from the aquatic environment is critical for preventing eutrophication and providing P resources. The activated iron system (mainly consisted of zero-valent iron (ZVI), Fe 3 O 4 and Fe 2+ ) has been reported to exhibit a favorable performance towards various contaminants in wastewater, but its effect on P recovery has not been studied systematically. In this study, we used Fe 2+ -nitrate pretreatment reaction to prepare the activated iron system and then applied it to P recovery. Results show that more than 99% P was removed from water in 60 min; co-existing anions (NO 3 - , Cl - and SO 4 2- ) and natural organic matter (NOM) had little effect on P removal. The P removal capacity of activated iron system is very high compared with currently reported sorbents. Externally-supplied Fe 2+ plays an important role on P removal in the system. Regeneration study shows that the activated iron system exhibited stable P recovery ability by using 0.1 M NaOH solution. Various methods were applied to characterize the ZVI and iron corrosion, and results conclude that sorption precipitation, and co-precipitation contribute to P removal. This method will be promising and have an application potential in the field for efficient and cost-effective recovery of P with cheap microscale zero valent iron. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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

Jin, Xiaoying; Chen, Zhengxian; Zhou, Rongbing

2015-01-15

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

Effect of bicarbonate on aging and reactivity of nanoscale zerovalent iron (nZVI) toward uranium removal.

PubMed

Hua, Yilong; Wang, Wei; Huang, Xiaoyue; Gu, Tianhang; Ding, Dexin; Ling, Lan; Zhang, Wei-Xian

2018-06-01

Bicarbonate, ubiquitous in natural and waste waters is an important factor regulating the rate and efficiency of pollutant separation and transformation. For example, it can form complexes with U(VI) in the aqueous phase and at the solid-water interface. In this work, we investigated the effect of bicarbonate on the aging of nanoscale zero-valent (nZVI) in the context of U(VI) reduction and removal from wastewater. For fresh nZVI, over 99% aqueous uranium was separated in less than 10 min, of which 83% was reduced from U(VI) to U(IV). When nZVI was aged in water, its activity for U(VI) sequestration and reduction was significantly reduced. Batch experiments showed that for nZVI aged in the presence of 10 mM bicarbonate, only 20.3% uranium was reduced to U(IV) after 6 h reactions. Characterizations of the iron nanoparticles with spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) suggest that in fresh nZVI, uranium was concentrated at the nanoparticle center; whereas in nZVI aged in bicarbonate, uranium was largely deposited on the outer surface of the nanoparticles. Furthermore, aged nZVI without bicarbonate contained more lepidocrocite (γ-FeOOH) while aged nZVI in the presence of bicarbonate had more magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ). This could be attributed to the formation of carbonate green rust and pH buffer effect of . Primary mechanisms for U(VI) removal with nZVI include reduction, sorption and/or precipitation. Results demonstrate that bicarbonate alter the aging products of nZVI, and reduces the separation efficiency and reduction capability for uranium removal. Copyright © 2018. Published by Elsevier Ltd.

Missing Fe: hydrogenated iron nanoparticles

NASA Astrophysics Data System (ADS)

Bilalbegović, G.; Maksimović, A.; Mohaček-Grošev, V.

2017-03-01

Although it was found that the FeH lines exist in the spectra of some stars, none of the spectral features in the interstellar medium (ISM) have been assigned to this molecule. We suggest that iron atoms interact with hydrogen and produce Fe-H nanoparticles which sometimes contain many H atoms. We calculate infrared spectra of hydrogenated iron nanoparticles using density functional theory methods and find broad, overlapping bands. Desorption of H2 could induce spinning of these small Fe-H dust grains. Some of hydrogenated iron nanoparticles possess magnetic and electric moments and should interact with electromagnetic fields in the ISM. FenHm nanoparticles could contribute to the polarization of the ISM and the anomalous microwave emission. We discuss the conditions required to form FeH and FenHm in the ISM.

Enhancing dewaterability of waste activated sludge by combined oxidative conditioning process with zero-valent iron and peroxymonosulfate.

PubMed

Zhou, Xu; Jin, Wenbiao; Chen, Hongyi; Chen, Chuan; Han, Songfang; Tu, Renjie; Wei, Wei; Gao, Shu-Hong; Xie, Guo-Jun; Wang, Qilin

2017-11-01

The enhancement of sludge dewaterability is of great importance for facilitating the sludge disposal during the operation of wastewater treatment plants. In this study, a novel oxidative conditioning approach was applied to enhance the dewaterability of waste activated sludge by the combination of zero-valent iron (ZVI) and peroxymonosulfate (PMS). It was found that the dewaterability of sludge was significantly improved after the addition of ZVI (0-4 g/g TSS) (TSS: total suspended solids) and PMS (0-1 g/g TSS). The optimal addition amount of ZVI and PMS was 0.25 g/g TSS and 0.1 g/g TSS, respectively, under which the capillary suction time of the sludge was reduced by approximately 50%. The decomposition of sludge flocs could contribute to the improved sludge dewaterability. Economic analysis demonstrated that the proposed conditioning process with ZVI and PMS was more economical than the ZVI + peroxydisulfate and the traditional Fenton conditioning processes.

Removal of polycyclic aromatic hydrocarbons (PAHs) from textile dyeing sludge by ultrasound combined zero-valent iron/EDTA/Air system.

PubMed

Man, Xiaoyuan; Ning, Xun-An; Zou, Haiyuan; Liang, Jieying; Sun, Jian; Lu, Xingwen; Sun, Jiekui

2018-01-01

This paper proposes a combined ultrasound (US) and zero-valent iron/EDTA/Air (ZEA) system to remove polycyclic aromatic hydrocarbons (PAHs) from textile dyeing sludge. The removal efficiencies of 16 PAHs using ZEA, US/Air (air injected into the US process), and US/ZEA treatments were investigated, together with the effects of various operating parameters. The enhanced mechanisms of US and the role of reactive oxygen species (ROS) in removing PAHs in the US/ZEA system were explored. Results showed that only 42.5% and 32.9% of ∑16 PAHs were removed by ZEA and US/Air treatments respectively, whereas 70.1% were removed by US/ZEA treatment, (with favorable operating conditions of 2.0 mM EDTA, 15 g/L ZVI, and 1.08 w/cm 3 ultrasonic density). The US/ZEA system could be used with a wide pH range. US led to synergistic improvement of PAHs removal in the ZEA system by enhancing sludge disintegration to release PAHs and promoting ZVI corrosion and oxygen activation. In the US/ZEA system, PAHs could be degraded by ROS (namely OH, O 2 - /HO 2 , and Fe(IV)) and adsorbed by ZVI, during which the ROS made the predominant contribution. This study provides important insights into the application of a US/ZEA system to remove PAHs from sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ammonium iron(III) phosphate(V) fluoride, (NH4)0.5[(NH4)0.375K0.125]FePO4F, with ammonium partially substituted by potassium

PubMed Central

Wang, Lei; Zhou, Yan; Huang, Ya-Xi; Mi, Jin-Xiao

2009-01-01

The title compound, ammonium potassium iron(III) phosphate fluoride, (NH4)0.875K0.125FePO4F, is built from zigzag chains ∞ 1{[FeO4F2]7−}, with Fe3+ in a distorted octahedral coordination, extending along both the [011] and [01] directions. These chains are made up of alternating trans-[FeO4F2] and cis-[FeO4F2] octa­hedra via shared F-atom corners, and are linked by PO4 tetra­hedra, resulting in an open-framework structure with channels along the [010] and [100] directions. There are two crystallographically independent ammonium sites: one in the [010] channels and the other, partially substituted by K+ ions, in the [100] channels. The ammonium in the [010] channels is fixed to the framework via eight hydrogen bonds (six N—H⋯O and two N—H⋯F). PMID:21581466

Removal of chlorinated organic solvents from hydraulic fracturing wastewater by bare and entrapped nanoscale zero-valent iron.

PubMed

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

2018-04-01

With the increasing application of hydraulic fracturing, it is urgent to develop an effective and economically feasible method to treat the large volumes of fracturing wastewater. In this study, bare and entrapped nanoscale zero-valent iron (nZVI) were introduced for the removal of carbon tetrachloride (CT) and 1,1,2-trichloroethane (TCA) in model high-salinity fracturing wastewater. With increasing ionic strength (I) from Day-1 (I = 0.35 M) to Day-90 (I = 4.10 M) wastewaters, bare nZVI presented significantly lower removal efficiency of CT (from 53.5% to 38.7%) and 1,1,2-TCA (from 71.1% to 21.7%) and underwent more serious Fe dissolution from 1.31 ± 1.19% in Day-1 to 5.79 ± 0.32% in Day-90 wastewater. Particle aggregation induced by high ionic strength was primarily responsible for the lowered performance of nZVI due to less available reactive sites on nZVI surface. The immobilization of nZVI in alginate with/without polyvinyl alcohol provided resistance to particle aggregation and contributed to the superior performance of entrapped nZVI in Day-90 wastewater for 1,1,2-TCA removal (62.6-72.3%), which also mitigated Fe dissolution (4.00-4.69%). Both adsorption (by polymer matrix) and reduction (by immobilized nZVI) were involved in the 1,1,2-TCA removal by entrapped nZVI. However, after 1-month immersion in synthetic fracturing wastewater, a marked drop in the reactivity of entrapped nZVI for 1,1,2-TCA removal from Day-90 wastewater was observed with significant release of Na and total organic carbon. In summary, bare nZVI was sensitive to the nature of the fracturing wastewater, while the use of environmentally benign entrapped nZVI was more promising for wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced removal of Se(VI) from water via pre-corrosion of zero-valent iron using H2O2/HCl: Effect of solution chemistry and mechanism investigation.

PubMed

Shan, Chao; Chen, Jiajia; Yang, Zhe; Jia, Huichao; Guan, Xiaohong; Zhang, Weiming; Pan, Bingcai

2018-04-15

Although the removal of Se(VI) from water by using zero-valent iron (ZVI) is a promising method, passivation of ZVI severely inhibits its performance. To overcome such issue, we proposed an efficient technique to enhance Se(VI) removal via pre-corrosion of ZVI with H 2 O 2 /HCl in a short time (15 min). The resultant pcZVI suspension was weakly acidic (pH 4.56) and contained abundant aqueous Fe 2+ . 57 Fe Mössbauer spectroscopy showed that pcZVI mainly consisted of Fe 0 (66.2%), hydrated ferric oxide (26.3%), and Fe 3 O 4 (7.5%). Efficient removal of Se(VI) from sulfate-rich solution was achieved by pcZVI compared with ZVI (in the absence and presence of H 2 O 2 ) and acid-pretreated ZVI. Moreover, the efficient removal of Se(VI) by pcZVI sustained over a broad pH range (3-9) due to its strong buffering power. The presence of chloride, carbonate, nitrate, and common cations (Na + , K + , Ca 2+ , and Mg 2+ ) posed negligible influence on the removal of Se(VI) by pcZVI, while the inhibitory effect induced by sulfate, silicate, and phosphate indicated the significance of Se(VI) adsorption as a prerequisite step for its removal. The consumption of aqueous Fe 2+ was associated with Se(VI) removal, and X-ray absorption near edge structure revealed that the main pathway for Se(VI) removal by pcZVI was a stepwise reduction of Se(VI) to Se(IV) and then Se 0 as the dominant final state (78.2%). Moreover, higher electron selectivity of pcZVI was attributed to the enhanced enrichment of Se oxyanions prior to their reduction. Copyright © 2018 Elsevier Ltd. All rights reserved.

THE APPLICATION OF IN SITU PERMEABLE REACTIVE (ZERO-VALENT IRON) BARRIER TECHNOLOGY FOR THE REMEDIATION OF CHROMATE-CONTAMINATED GROUNDWATER: A FIELD TEST

EPA Science Inventory

A small-scale field test was initiated in September 1994 to evaluate the in situ remediation of groundwater contaminated with chromate using a permeable reactive barrier composed of a mixture of zero-valent Fe, sand and aquifer sediment. The site used was an old chrome-plating f...

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

PubMed

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

2012-12-01

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

Structural and magnetic properties of FeHx (x=0.25; 0.50; 0.75)

NASA Astrophysics Data System (ADS)

Mikhaylushkin, A. S.; Skorodumova, N. V.; Ahuja, R.; Johansson, B.

2006-05-01

The structural and magnetic properties of the FeHx (x=0.25; 0.50; 0.75) compounds have been studied using the projector augmented wave (PAW) method within the generalized gradient approximation (GGA). We compare the hcp, dhcp and fcc structures and find that for the considered concentrations of hydrogen the hcp structure is most stable in a wide pressure range. The magnetic behavior of iron is crucially influenced by hydrogen. In particular, the local moment on a Fe atom depends on the number of hydrogen atoms in the atom surroundings. Iron atoms, which are crystallographically equivalent in their original structures (hcp, fcc) but have different number of hydrogen neighbors, are shown to have different local magnetic moments. This finding suggests that the experimental observations of two magnetic moments in iron hydride can be explained by nonstoichiometry of the hydride and might not be a direct evidence for the presence of the dhcp phase.

Enhanced Formation of Oxidants from Bimetallic Nickel-Iron Nanoparticles in the Presence of Oxygen

PubMed Central

Lee, Changha; Sedlak, David L.

2009-01-01

Nanoparticulate zero-valent iron (nZVI) rapidly reacts with oxygen to produce strong oxidants, capable of transforming organic contaminants in water. However, the low yield of oxidants with respect to the iron added normally limits the application of this system. Bimetallic nickel-iron nanoparticles (nNi-Fe; i.e., Ni-Fe alloy and Ni-coated Fe nanoparticles) exhibited enhanced yields of oxidants compared to nZVI. nNi-Fe (Ni-Fe alloy nanoparticles with [Ni]/[Fe] = 0.28 and Ni-coated Fe nanoparticles with [Ni]/[Fe] = 0.035) produced approximately 40% and 85% higher yields of formaldehyde from the oxidation of methanol relative to nZVI at pH 4 and 7, respectively. Ni-coated Fe nanoparticles showed a higher efficiency for oxidant production relative to Ni-Fe alloy nanoparticles based on Ni content. Addition of Ni did not enhance the oxidation of 2-propanol or benzoic acid, indicating that Ni addition did not enhance hydroxyl radical formation. The enhancement in oxidant yield was observed over a pH range of 4 – 9. The enhanced production of oxidant by nNi-Fe appears to be attributable to two factors. First, the nNi-Fe surface is less reactive toward hydrogen peroxide (H2O2) than the nZVI surface, which favors the reaction of H2O2 with dissolved Fe(II) (the Fenton reaction). Second, the nNi-Fe surface promotes oxidant production from the oxidation of ferrous ion by oxygen at neutral pH values. PMID:19068843

Analytical Characterisation of Nanoscale Zero-Valent Iron: A ...

EPA Pesticide Factsheets

Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their tendency to aggregate. Both the mobility and reactivity of nZVI mainly depends on properties such as particle size, surface chemistry and bulk composition. In order to ensure efficient remediation, it is crucial to accurately assess and understand the implications of these properties before deploying these materials into contaminated environments. Many analytical techniques are now available to determine these parameters and this paper provides a critical review of their usefulness and limitations for nZVI characterisation. These analytical techniques include microscopy and light scattering techniques for the determination of particle size, size distribution and aggregation state, and X-ray techniques for the characterisation of surface chemistry and bulk composition. Example characterisation data derived from commercial nZVI materials is used to further illustrate method strengths and limitations. Finally, some important challenges with respect to the characterisation of nZVI in groundwater samples are discussed. In recent years, manufactured nanoparticles (MNPs) have attracted increasing interest for their potential applications in the treatment of contaminated soil and water. In compar

Arsenic removal with composite iron matrix filters in Bangladesh: a field and laboratory study.

PubMed

Neumann, Anke; Kaegi, Ralf; Voegelin, Andreas; Hussam, Abul; Munir, Abul K M; Hug, Stephan J

2013-05-07

The main arsenic mitigation measures in Bangladesh, well-switching and deep tube wells, have reduced As exposure, but water treatment is important where As-free water is not available. Zero-valent iron (ZVI) based SONO household filters, developed in Bangladesh, remove As by corrosion of locally available inexpensive surplus iron and sand filtration in two buckets. We investigated As removal in SONO filters in the field and laboratory, covering a range of typical groundwater concentrations (in mg/L) of As (0.14-0.96), Fe (0-17), P (0-4.4), Ca (45-162), and Mn (0-2.8). Depending on influent Fe(II) concentrations, 20-80% As was removed in the top sand layer, but As removal to safe levels occurred in the ZVI-layer of the first bucket. Residual As, Fe, and Mn were removed after re-aeration in the sand of the second bucket. New and over 8-year-old filters removed As to <50 μg/L and mostly to <10 μg/L and Mn to <0.2 mg/L. Vertical concentration profiles revealed formation of Fe(II) by corrosion of Fe(0) with O2 and incorporation of As into forming amorphous Fe phases in the composite iron matrix (CIM) of newer filters and predominantly magnetite in older filters. As mass balances indicated that users filtered less than reported volumes of water, pointing to the need for more educational efforts. All tested SONO filters provided safe drinking water without replacement for up to over 8 years of use.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

Effects of Pnictogen Atmosphere Annealing on Fe1+yTe0.6Se0.4

NASA Astrophysics Data System (ADS)

Yamada, Tatsuhiro; Sun, Yue; Pyon, Sunseng; Tamegai, Tsuyoshi

2016-02-01

It has been clarified that bulk superconductivity in Fe1+yTe0.6Se0.4 can be induced by annealing in an appropriate atmosphere to remove the harmful effects of excess iron. In order to clarify the details of the annealing process, we studied the changes in the physical properties and reaction products of Fe1+yTe0.6Se0.4 annealed in pnictogen (P, As, Sb) atmospheres. Crystals annealed in a pnictogen atmosphere show bulk superconductivity and the values of Tc and Jc are about 14 K and (2-4) × 105 A/cm2 (2 K, self-field), respectively. It is also found that the reaction rate increases with the increase in the saturated vapor pressure of the pnictogen. Unexpectedly, the reaction products of Fe1+yTe0.6Se0.4 after annealing in a P atmosphere mainly consist of FeTe2. In addition, the amount of P required to obtain the optimal Tc is much smaller than the amount of excess iron, which is similar to the case of oxygen annealing. P, oxygen, and to some extent As could serve as catalysts to form FeTe2 to remove excess iron.

Channel flow and trichloroethylene treatment in a partly iron-filled fracture: experimental and model results.

PubMed

Cai, Zuansi; Merly, Corrine; Thomson, Neil R; Wilson, Ryan D; Lerner, David N

2007-08-15

Technical developments have now made it possible to emplace granular zero-valent iron (Fe(0)) in fractured media to create a Fe(0) fracture reactive barrier (Fe(0) FRB) for the treatment of contaminated groundwater. To evaluate this concept, we conducted a laboratory experiment in which trichloroethylene (TCE) contaminated water was flushed through a single uniform fracture created between two sandstone blocks. This fracture was partly filled with what was intended to be a uniform thickness of iron. Partial treatment of TCE by iron demonstrated that the concept of a Fe(0) FRB is practical, but was less than anticipated for an iron layer of uniform thickness. When the experiment was disassembled, evidence of discrete channelised flow was noted and attributed to imperfect placement of the iron. To evaluate the effect of the channel flow, an explicit Channel Model was developed that simplifies this complex flow regime into a conceptualised set of uniform and parallel channels. The mathematical representation of this conceptualisation directly accounts for (i) flow channels and immobile fluid arising from the non-uniform iron placement, (ii) mass transfer from the open fracture to iron and immobile fluid regions, and (iii) degradation in the iron regions. A favourable comparison between laboratory data and the results from the developed mathematical model suggests that the model is capable of representing TCE degradation in fractures with non-uniform iron placement. In order to apply this Channel Model concept to a Fe(0) FRB system, a simplified, or implicit, Lumped Channel Model was developed where the physical and chemical processes in the iron layer and immobile fluid regions are captured by a first-order lumped rate parameter. The performance of this Lumped Channel Model was compared to laboratory data, and benchmarked against the Channel Model. The advantages of the Lumped Channel Model are that the degradation of TCE in the system is represented by a first

Channel flow and trichloroethylene treatment in a partly iron-filled fracture: Experimental and model results

NASA Astrophysics Data System (ADS)

Cai, Zuansi; Merly, Corrine; Thomson, Neil R.; Wilson, Ryan D.; Lerner, David N.

2007-08-01

Technical developments have now made it possible to emplace granular zero-valent iron (Fe 0) in fractured media to create a Fe 0 fracture reactive barrier (Fe 0 FRB) for the treatment of contaminated groundwater. To evaluate this concept, we conducted a laboratory experiment in which trichloroethylene (TCE) contaminated water was flushed through a single uniform fracture created between two sandstone blocks. This fracture was partly filled with what was intended to be a uniform thickness of iron. Partial treatment of TCE by iron demonstrated that the concept of a Fe 0 FRB is practical, but was less than anticipated for an iron layer of uniform thickness. When the experiment was disassembled, evidence of discrete channelised flow was noted and attributed to imperfect placement of the iron. To evaluate the effect of the channel flow, an explicit Channel Model was developed that simplifies this complex flow regime into a conceptualised set of uniform and parallel channels. The mathematical representation of this conceptualisation directly accounts for (i) flow channels and immobile fluid arising from the non-uniform iron placement, (ii) mass transfer from the open fracture to iron and immobile fluid regions, and (iii) degradation in the iron regions. A favourable comparison between laboratory data and the results from the developed mathematical model suggests that the model is capable of representing TCE degradation in fractures with non-uniform iron placement. In order to apply this Channel Model concept to a Fe 0 FRB system, a simplified, or implicit, Lumped Channel Model was developed where the physical and chemical processes in the iron layer and immobile fluid regions are captured by a first-order lumped rate parameter. The performance of this Lumped Channel Model was compared to laboratory data, and benchmarked against the Channel Model. The advantages of the Lumped Channel Model are that the degradation of TCE in the system is represented by a first

KMg0.09Fe1.91(PO4)2

PubMed Central

Yatskin, Michael M.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Ogorodnyk, Ivan V.; Slobodyanik, Nikolay S.

2012-01-01

KMg0.09Fe1.91(PO4)2, potassium [iron(II)/magnesium] iron(III) bis(orthophosphate), is a solid solution derived from compounds with general formula KM IIFe(PO4)2 (M II = Fe, Cu), in which the Mg atoms substitute Fe atoms only in the octa­hedrally surrounded sites. The framework of the structure is built up from [FeO5] trigonal bipyramids and [MO6] (M = (Fe, Mg) octa­hedra sharing corners and edges and connected by two types of bridging PO4 tetra­hedra. The K+ cations are nine-coordinated and are situated in channels running along [101]. PMID:22719280

Surface coating with Ca(OH)2 for improvement of the transport of nanoscale zero-valent iron (nZVI) in porous media.

PubMed

Wei, Cai-jie; Li, Xiao-yan

2013-01-01

A novel thermal deposition method was developed to coat Ca(OH)2 on the surface of nanoscale zero-valent iron (nZVI). The nZVI particles with the Ca(OH)2 coating layer, nZVI/Ca(OH)2, had a clear core-shell structure based on the transmission electron microscopy observations, and the Ca(OH)2 shell was identified as an amorphous phase. The Ca(OH)2 coating shell would not only function as an effective protection layer for nZVI but also improve the mobility of nZVI in porous media for its use in environmental decontamination. A 10% Ca/Fe mass ratio was found to result in a proper thickness of the Ca(OH)2 shell on the nZVI surface. Based on the filtration tests in sand columns, the Ca(OH)2-based surface coating could greatly improve the mobility and transport of nZVI particles in porous media. In addition, batch experiments were conducted to evaluate the reactivity of Ca(OH)2-coated nZVI particles for the reduction of Cr(VI) and its removal from water.

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

NASA Astrophysics Data System (ADS)

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

2013-09-01

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

Removal of Cr(VI) from groundwater by Fe(0)

NASA Astrophysics Data System (ADS)

Gao, Yanjiao; Liu, Rui

2017-11-01

This research was conducted to investigate the treatment of hexavalent chromium (Cr(VI)) by iron powder (Fe(0)) columns of simulated permeable reactive barriers with and without calcium carbonate (CaCO3). Two columns filled with Fe(0) were used as Cr(VI) removal equipment running at a flow velocity of 10 ml/min at room temperature. After 200 days running of the two columns, the results showed that Fe(0) was an effective material for Cr(VI) reduction with an average removal rate of above 84.6%. The performance of Column 2 with CaCO3 was better than Column 1 without CaCO3 in terms of average Cr(VI) removal rate. The presence of CaCO3 buffered the increasing pH caused by Fe(0) corrosion in Column 2 and enhanced the removal rate of Column 2. Scanning Electron Microscopy (SEM) images of Fe(0) in the three stages of running of the two columns illustrated that the coat layer of Column 1 was a little thicker than that of Column 2. Energy-dispersive spectrometry (EDS) results showed that the surface of Fe(0) of Column 2 contained more chromium elements. Raman spectroscopy found that all iron oxide was generated on the Fe(0) surface of Column 1 and Column 2 and chromium class objects were only detected on Fe(0) surface in Column 2.

Simultaneous removal of nitrate, hydrogen peroxide and phosphate in semiconductor acidic wastewater by zero-valent iron.

PubMed

Yoshino, Hiroyuki; Tokumura, Masahiro; Kawase, Yoshinori

2014-01-01

The zero-valent iron (ZVI) wastewater treatment has been applied to simultaneous removal of nitrate, hydrogen peroxide and phosphate in semiconductor acidic wastewaters. The simultaneous removal occurs by the reactions performed due to the sequential transformation of ZVI under the acidic condition. Fortunately the solution pH of semiconductor acidic wastewaters is low which is effective for the sequential transformation of ZVI. Firstly the reduction of nitrate is taken place by electrons generated by the corrosion of ZVI under acidic conditions. Secondly the ferrous ion generated by the corrosion of ZVI reacts with hydrogen peroxide and generates ·OH radical (Fenton reaction). The Fenton reaction consists of the degradation of hydrogen peroxide and the generation of ferric ion. Finally phosphate precipitates out with iron ions. In the simultaneous removal process, 1.6 mM nitrate, 9.0 mM hydrogen peroxide and 1.0 mM phosphate were completely removed by ZVI within 100, 15 and 15 min, respectively. The synergy among the reactions for the removal of nitrate, hydrogen peroxide and phosphate was found. In the individual pollutant removal experiment, the removal of phosphate by ZVI was limited to 80% after 300 min. Its removal rate was considerably improved in the presence of hydrogen peroxide and the complete removal of phosphate was achieved after 15 min.

Orbital superconductivity, defects, and pinned nematic fluctuations in the doped iron chalcogenide FeSe 0.45 Te 0.55

DOE PAGES

Sarkar, Saheli; Van Dyke, John; Sprau, Peter O.; ...

2017-08-09

We demonstrate that the differential conductance, dI/dV , measured via spectroscopic imaging scanning tunneling microscopy in the doped iron chalcogenide FeSe0.45Te0.55, possesses a series of characteristic features that allow one to extract the orbital structure of the superconducting gaps. This yields nearly isotropic superconducting gaps on the two hole-like Fermi surfaces, and a strongly anisotropic gap on the electron-like Fermi surface. Moreover, we show that the pinning of nematic fluctuations by defects can give rise to a dumbbell-like spatial structure of the induced impurity bound states, and explains the related C 2-symmetry in the Fourier transformed differential conductance.

Orbital superconductivity, defects, and pinned nematic fluctuations in the doped iron chalcogenide FeSe 0.45 Te 0.55

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

Sarkar, Saheli; Van Dyke, John; Sprau, Peter O.

We demonstrate that the differential conductance, dI/dV , measured via spectroscopic imaging scanning tunneling microscopy in the doped iron chalcogenide FeSe0.45Te0.55, possesses a series of characteristic features that allow one to extract the orbital structure of the superconducting gaps. This yields nearly isotropic superconducting gaps on the two hole-like Fermi surfaces, and a strongly anisotropic gap on the electron-like Fermi surface. Moreover, we show that the pinning of nematic fluctuations by defects can give rise to a dumbbell-like spatial structure of the induced impurity bound states, and explains the related C 2-symmetry in the Fourier transformed differential conductance.

Orbital superconductivity, defects, and pinned nematic fluctuations in the doped iron chalcogenide FeSe 0.45 Te 0.55

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

Sarkar, Saheli; Van Dyke, John; Sprau, Peter O.

We demonstrate that the differential conductance, dI/dV, measured via spectroscopic imaging scanning tunneling microscopy in the doped iron chalcogenide FeSe0.45Te0.55, possesses a series of characteristic features that allow one to extract the orbital structure of the superconducting gaps. This yields nearly isotropic superconducting gaps on the two holelike Fermi surfaces, and a strongly anisotropic gap on the electronlike Fermi surface. Moreover, we show that the pinning of nematic fluctuations by defects can give rise to a dumbbell-like spatial structure of the induced impurity bound states, and explains the related C-2 symmetry in the Fourier transformed differential conductance.

Coexistence of superconductivity and antiferromagnetism in (Li0.8Fe0.2)OHFeSe.

PubMed

Lu, X F; Wang, N Z; Wu, H; Wu, Y P; Zhao, D; Zeng, X Z; Luo, X G; Wu, T; Bao, W; Zhang, G H; Huang, F Q; Huang, Q Z; Chen, X H

2015-03-01

Iron selenide superconductors exhibit a number of unique characteristics that are helpful for understanding the mechanism of superconductivity in high-Tc iron-based superconductors more generally. However, in the case of AxFe2Se2 (A = K, Rb, Cs), the presence of an intergrown antiferromagnetic insulating phase makes the study of the underlying physics problematic. Moreover, FeSe-based systems intercalated with alkali metal ions, NH3 molecules or organic molecules are extremely sensitive to air, which prevents the further investigation of their physical properties. It is therefore desirable to find a stable and easily accessible FeSe-based superconductor to study its physical properties in detail. Here, we report the synthesis of an air-stable material, (Li0.8Fe0.2)OHFeSe, which remains superconducting at temperatures up to ~40 K, by means of a novel hydrothermal method. The crystal structure is unambiguously determined by a combination of X-ray and neutron powder diffraction and nuclear magnetic resonance. Moreover, antiferromagnetic order is shown to coexist with superconductivity. This synthetic route opens a path for exploring superconductivity in other related systems, and confirms the appeal of iron selenides as a platform for understanding superconductivity in iron pnictides more broadly.

Degradation of trichloroethene with a noval ball milled Fe-C nanocomposite

DOE PAGES

Gao, Jie; Wang, Wei; Rondinone, Adam Justin; ...

2015-07-18

Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron-carbon (Fe-C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbedmore » >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe-C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C 3-C 6 compounds. When placed in hexane-water mixture, the Fe-C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.« less

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

PubMed

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

2015-11-01

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

Investigating the mechanism of clofibric acid removal in Fe(0)/H2O systems.

PubMed

Ghauch, Antoine; Abou Assi, Hala; Tuqan, Almuthanna

2010-04-15

Since the introduction of iron wall technology, the inherent relationship between contaminant removal and iron corrosion has been mostly attributed to electron transfer from the metal body (direct reduction). This thermodynamically founded premise has failed to explain several experimental facts. Recently, a new concept considering adsorption and co-precipitation as fundamental contaminant removal mechanisms was introduced. This consistent concept has faced very skeptic views and necessarily needs experimental validation. The present work was the first independent attempt to validate the new concept using clofibric acid (CLO) as model compound. For this purpose, a powdered Fe(0) material (Fe(0)) was used in CLO removal experiments under various experimental conditions. Additional experiments were performed with plated Fe(0) (mFe(0): Fe(0)/Pd(0), Fe(0)/Ni(0)) to support the discussion of removal mechanism. Main investigated experimental variables included: abundance of O(2), abundance of iron corrosion products (ICPs) and shaking operations. Results corroborated the concept that quantitative contaminant removal in Fe(0)/H(2)O systems occurs within the oxide-film in the vicinity of Fe(0). Additionally, mixing type and shaking intensity significantly influenced the extent of CLO removal. More importantly, HPLC/MS revealed that the identity of reaction products depends on the extent of iron corrosion or the abundance of ICPs. The investigation of the CLO/Fe(0)/H(2)O system disproved the popular view that direct reduction mediates contaminant removal in the presence of Fe(0). 2009 Elsevier B.V. All rights reserved.

High-pressure and high-temperature phase diagram for Fe0.9Ni0.1-H alloy

NASA Astrophysics Data System (ADS)

Shibazaki, Yuki; Terasaki, Hidenori; Ohtani, Eiji; Tateyama, Ryuji; Nishida, Keisuke; Funakoshi, Ken-ichi; Higo, Yuji

2014-03-01

Planetary cores are considered to consist of an iron-nickel (Fe-Ni) alloy and light elements and hydrogen is one of plausible light elements in the core. Here we have performed in situ X-ray diffraction experiments on an Fe0.9Ni0.1-H system up to 15.1 GPa and 1673 K, and investigated the effect of Ni on phase relations of FeHx under high pressure and high temperature. The experimental system in the present work was oversaturated with hydrogen. We found a face-center-cubic (fcc) phase (with hydrogen concentration up to x∼1) and a body-center-cubic (bcc) phase (x < 0.1) as stable phases. The partial melting was observed below 6 GPa. We could not observe a double-hexagonal-close-packed (dhcp) phase because of limitations in pressure and temperature conditions. The stability field of each phase of Fe0.9Ni0.1Hx was almost same as that of FeHx. The solidus of Fe0.9Ni0.1Hx was 500-700 K lower than the melting curve of Fe and its liquidus was 400-600 K lower than that of Fe in the pressure range of this study. Both the solidus and liquidus of Fe0.9Ni0.1Hx were depressed at around 3.5 GPa, as was the solidus of FeHx. The hydrogen contents in fcc-Fe0.9Ni0.1Hx just below solidus were slightly lower than those of fcc-FeHx, which suggests that nickel is likely to prevent dissolution of hydrogen into iron. Due to the lower hydrogen solubilities in Fe0.9Ni0.1 compared to Fe, the solidus of Fe0.9Ni0.1Hx is about 100-150 K higher than that of FeHx.

Tailoring the properties of a zero-valent iron-based composite by mechanochemistry for nitrophenols degradation in wastewaters.

PubMed

Cagnetta, Giovanni; Huang, Jun; Lomovskiy, Igor O; Yu, Gang

2017-11-01

Zero-valent iron (ZVI) is a valuable material for environmental remediation, because of its safeness, large availability, and inexpensiveness. Moreover, its reactivity can be improved by addition of (nano-) particles of other elements such as noble metals. However, common preparation methods for this kind of iron-based composites involve wet precipitation of noble metal salt precursors, so they are often expensive and not green. Mechanochemical procedures can provide a solvent-free alternative, even at a large scale. The present study demonstrates that it is possible to tailor functional properties of ZVI-based materials, utilizing high-energy ball milling. All main preparation parameters are investigated and discussed. Specifically, a copper-carbon-iron ternary composite was prepared for fast degradation of 4-nitrophenol (utilized as model pollutant) to 4-aminophenol and other phenolic compounds. Copper and carbon are purposely chosen to insert specific properties to the composite: Copper acts as efficient nano-cathode that enhances electron transfer from iron to 4-nitrophenol, while carbon protects the iron surface from fast oxidation in open air. In this way, the reactive material can rapidly reduce high concentration of nitrophenols in water, it does not require acid washing to be activated, and can be stored in open air for one week without any significant activity loss.

Use of zero-valent iron biosand filters to reduce E. coli O157:H12 in irrigation water applied to spinach plants in a field setting

USDA-ARS?s Scientific Manuscript database

Introduction: Zero-valent iron (ZVI) filters may provide an efficient method to mitigate the contamination of produce crops through irrigation water. Purpose: To evaluate the use of ZVI-filtration in decontaminating E. coli O157:H12 in irrigation water and on spinach plants in a small, field-scale...

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

PubMed Central

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-01-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water. PMID:27095387

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

NASA Astrophysics Data System (ADS)

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-04-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

The catalytic center of ferritin regulates iron storage via Fe(II)-Fe(III) displacement.

PubMed

Honarmand Ebrahimi, Kourosh; Bill, Eckhard; Hagedoorn, Peter-Leon; Hagen, Wilfred R

2012-11-01

A conserved iron-binding site, the ferroxidase center, regulates the vital iron storage role of the ubiquitous protein ferritin in iron metabolism. It is commonly thought that two Fe(II) simultaneously bind the ferroxidase center and that the oxidized Fe(III)-O(H)-Fe(III) product spontaneously enters the cavity of ferritin as a unit. In contrast, in some bacterioferritins and in archaeal ferritins a persistent di-iron prosthetic group in this center is believed to mediate catalysis of core formation. Using a combination of binding experiments and isotopically labeled (57)Fe(II), we studied two systems in comparison: the ferritin from the hyperthermophilic archaeal anaerobe Pyrococcus furiosus (PfFtn) and the eukaryotic human H ferritin (HuHF). The results do not support either of the two paradigmatic models; instead they suggest a unifying mechanism in which the Fe(III)-O-Fe(III) unit resides in the ferroxidase center until it is sequentially displaced by Fe(II).

Ba2F2Fe2+ 0.5Fe3+ S3: a two-dimensional inhomogeneous mixed valence iron compound.

PubMed

Kabbour, Houria; Cario, Laurent

2008-03-03

The structure of the new mixed valence compound Ba2F2Fe1.5S3 was solved by means of single crystal X-ray analysis. It crystallizes in an orthorhombic cell, in the Pnma space group with the cell parameters a = 12.528(3) A, b = 18.852(4) A, and c = 6.0896(12) A. The structure is formed by the alternated stacking of fluorite type [Ba2F2]2+ blocks and the newly discovered [Fe1.5S3]2- blocks. This [Fe1.5S3]2- block exhibits a mixed valence of iron with Fe(+II) located in octahedrons and Fe(+III) in tetrahedrons. Preliminary susceptibility measurements suggest a low dimensional antiferromagnetic behavior.

The use of Zero-valent iron biosand filters to reduce E. coli O157:H12 in irrigation water applied to spinach plants in a field setting

USDA-ARS?s Scientific Manuscript database

Contaminated irrigation water is a potential source for the introduction of foodborne pathogens on to produce commodities. Zero-valent iron (ZVI) may provide a simple cheap method to mitigate the contamination of produce groups through irrigation water. A small field scale system was utilized to e...

TREATMENT OF 1,2-DIBROMO-3-CHLOROPROPANE AND NITRATE-CONTAMINATED WATER WITH ZERO-VALENT IRON OR HYDROGEN/PALLADIUM CATALYSTS. (R825689C054,R825689C078)

EPA Science Inventory

Abstract

The abilities of zero-valent iron powder and hydrogen with a palladium catalyst (H₂/Pd-alumina) to hydrodehalogenate 1,2-dibromo-3-chloropropane (DBCP) to propane under water treatment conditions (ambient temperature and circumneutral pH) were compa...

Enhanced superconductivity in surface-electron-doped iron pnictide Ba(Fe 1.94Co 0.06) 2As 2

DOE PAGES

Kyung, W. S.; Huh, S. S.; Koh, Y. Y.; ...

2016-08-15

The transition critical temperature (TC ) in a FeSe monolayer on SrTiO 3 is enhanced up to 100 K. High TC is also found in bulk iron chalcogenides with similar electronic structure to that of monolayer FeSe, which suggests that higher TC may be achieved through electron doping, pushing the Fermi surface (FS) topology towards leaving only electron pockets. Such observation, however, has been limited to chalcogenides and is in contrast with the iron pnictides for which the maximum TC is achieved with both hole and electron pockets forming considerable FS nesting instability. Here, we report angle-resolved photoemission (ARPES) characterizationmore » revealing a monotonic increase of TC from 24 to 41.5 K upon surface doping on optimally doped Ba(Fe 1-xCo x) 2As 2 . The doping changes the overall FS topology towards that of chalcogenides through a rigid downward band shift. Our findings suggest that higher electron doping and concomitant changes in FS topology are favorable conditions for the superconductivity, not only for iron chalcogenides but also for iron pnictides.« less

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

Simultaneous removal of cadmium and nitrate in aqueous media by nanoscale zerovalent iron (nZVI) and Au doped nZVI particles.

PubMed

Su, Yiming; Adeleye, Adeyemi S; Huang, Yuxiong; Sun, Xiaoya; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei; Keller, Arturo A

2014-10-15

Nanoscale zerovalent iron (nZVI) has demonstrated high efficacy for treating nitrate or cadmium (Cd) contamination, but its efficiency for simultaneous removal of nitrate and Cd has not been investigated. This study evaluated the reactivity of nZVI to the co-contaminants and by-product formation, employed different catalysts to reduce nitrite yield from nitrate, and examined the transformation of nZVI after reaction. Nitrate reduction resulted in high solution pH, negatively charged surface of nZVI, formation of Fe3O4 (a stable transformation of nZVI), and no release of ionic iron. Increased pH and negative charge contributed to significant increase in Cd(II) removal capacity (from 40 mg/g to 188 mg/g) with nitrate present. In addition, nitrate reduction by nZVI could be catalyzed by Cd(II): while 30% of nitrate was reduced by nZVI within 2 h in the absence of Cd(II), complete nitrate reduction was observed in the presence of 40 mg-Cd/L due to the formation of Cd islands (Cd(0) and CdO) on the nZVI particles. While nitrate was reduced mostly to ammonium when Cd(II) was not present or at Cd(II) concentrations ≥ 40 mg/L, up to 20% of the initial nitrate was reduced to nitrite at Cd(II) concentrations < 40 mg/L. Among nZVI particles doped with 1 wt. % Cu, Ag, or Au, nZVI deposited with 1 wt. % Au reduced nitrite yield to less than 3% of the initial nitrate, while maintaining a high Cd(II) removal capacity. Copyright © 2014 Elsevier Ltd. All rights reserved.

ARSENIC INTERACTION WITH IRON (II, III) HYDROXYCARBONATE GREEN RUST: IMPLICATIONS FOR ARSENIC REMEDIATION

EPA Science Inventory

Zerovalent iron is being used in permeable reactive barriers (PRBs) to remediate groundwater arsenic contamination. Iron(II, III) hydroxycarbonate green rust is a major corrosion product of zerovalent iron under anaerobic conditions. The interaction between arsenic and this green...

Melting of Fe and Fe0.9Ni0.1 alloy at high pressures

NASA Astrophysics Data System (ADS)

Zhang, D.; Jackson, J. M.; Zhao, J.; Sturhahn, W.; Alp, E. E.; Hu, M. Y.; Toellner, T.

2014-12-01

Cosmochemical studies suggest that the cores of terrestrial planets are primarily composed of Fe alloyed with about 5 to 10 wt% Ni, plus some light elements (e.g., McDonough and Sun 1995). Thus, the high pressure melting curve of Fe0.9Ni0.1 is considered to be an important reference for characterizing the cores of terrestrial planets. We have determined the melting points of fcc-structured Fe and Fe0.9Ni0.1 up to 86 GPa using an in-situ method that monitors the atomic dynamics of the Fe atoms in the sample, synchrotron Mössbauer spectroscopy (Jackson et al. 2013). A laser heated diamond anvil cell is used to provide the high pressure-high temperature environmental conditions, and in-situ X-ray diffraction is used to constrain the pressure of the sample. To eliminate the influence of temperature fluctuations experienced by the sample on the determination of melting, we develop a Fast Temperature Readout (FasTeR) spectrometer. The FasTeR spectrometer features a fast reading rate (>100 Hz), a high sensitivity, a large dynamic range and a well-constrained focus. By combining the melting curve of fcc-structured Fe0.9Ni0.1 alloy determined in our study and the fcc-hcp phase boundary from Komabayashi et al. (2012), we calculate the fcc-hcp-liquid triple point of Fe0.9Ni0.1. Using this triple point and the thermophysical parameters from a nuclear resonant inelastic X-ray scattering study on hcp-Fe (Murphy et al. 2011), we compute the melting curve of hcp-structured Fe0.9Ni0.1. We will discuss our new experimental results with implications for the cores of Venus, Earth and Mars. Select references: McDonough & Sun (1995): The composition of the Earth. Chem. Geol. 120, 223-253. Jackson et al. (2013): Melting of compressed iron by monitoring atomic dynamics, EPSL, 362, 143-150. Komabayashi et al. (2012): In situ X-ray diffraction measurements of the fcc-hcp phase transition boundary of an Fe-Ni alloy in an internally heated diamond anvil cell, PCM, 39, 329-338. Murphy et al

Design and characterization of sulfide-modified nanoscale zerovalent iron for cadmium(II) removal from aqueous solutions

NASA Astrophysics Data System (ADS)

Lv, Dan; Zhou, Xiaoxin; Zhou, Jiasheng; Liu, Yuanli; Li, Yizhou; Yang, Kunlun; Lou, Zimo; Baig, Shams Ali; Wu, Donglei; Xu, Xinhua

2018-06-01

Nanoscale zero-valent iron (nZVI) has high removal efficiency and strong reductive ability to organic and inorganic contaminants, but concerns over its stability and dispersity limit its application. In this study, nZVI was modified with sulfide to enhance Cd(II) removal from aqueous solutions. TEM and SEM analyses showed that sulfide-modified nZVI (S-nZVI) had a core-shell structure of nano-sized spherical particles, and BET results proved that sulfide modification doubled the specific surface area from 26.04 to 50.34 m2 g-1 and inhibited the aggregation of nZVI. Mechanism analysis indicated that Cd(II) was immobilized through complexation and precipitation. Cd(II) removal rate on nZVI was only 32% in 2 h, while complete immobilization could be achieved in 15 min on S-nZVI, and S-nZVI with an optimal S/Fe molar ratio of 0.3 offered a cadmium removal capacity of about 150 mg g-1 at pH 7 and 303 K. The process of Cd(II) immobilization on S-nZVI was fitted well with pseudo-second-order kinetic model, and the increase of temperature favored Cd(II) immobilization, suggesting an endothermic process. The presence of Mg2+ and Ca2+ hindered Cd(II) removal while Cu2+ did the opposite, which led to the order as Cu2+ > control > Mg2+ > Ca2+. The removal rate of 20 mg L-1 Cd(II) maintained a high level with the fluctuation of environmental conditions such as pH, ion strength and presence of HA. This study demonstrated that S-nZVI could be a promising adsorbent for Cd(II) immobilization from cadmium-contaminated water.

Effect of geochemical properties on degradation of trichloroethylene by stabilized zerovalent iron nanoparticle with Na-acrylic copolymer.

PubMed

Chen, Meng-yi; Su, Yuh-fan; Shih, Yang-hsin

2014-11-01

Stable nanoscale zero-valent iron (NZVI) particles have been developed to remediate chlorinated compounds. The degradation kinetics and efficiency of trichloroethylene (TCE) by a commercial stabilized NZVI with Na-acrylic copolymer (acNZVI) were investigated and compared with those by laboratory-synthesized NZVI and carboxymethyl cellulose (CMC)-stabilized NZVI particles. Results show that the degradation of TCE by acNZVI was faster than that by NZVI and CMC-NZVI. Increase in temperature enhanced the degradation rate and efficiency of TCE with acNZVI. The activation energy of TCE degradation by acNZVI was estimated to be 23 kJ/mol. The degradation rate constants of TCE decreased from 0.064 to 0.026 min(-1) with decrease in initial pH from 9.03 to 4.23. Common groundwater anions including NO3(-), Cl(-), HCO3(-), and SO4(2-) inhibited slightly the degradation efficiencies of TCE by acNZVI. The Na-acrylic copolymer-stabilized NZVI, which exhibited high degradation kinetics and efficiency, could be a good remediation agent for chlorinated organic compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Inhibiting excessive acidification using zero-valent iron in anaerobic digestion of food waste at high organic load rates.

PubMed

Kong, Xin; Wei, Yonghong; Xu, Shuang; Liu, Jianguo; Li, Huan; Liu, Yili; Yu, Shuyao

2016-07-01

Excessive acidification occurs frequently in food waste (FW) anaerobic digestion (AD) due to the high carbon-to-nitrogen ratio of FW. In this study, zero-valent iron (ZVI) was applied to prevent the excessive acidification. All of the control groups, without ZVI addition (pH∼5.3), produced little methane (CH4) and had high volatile fatty acids/bicarbonate alkalinity (VFA/ALK). By contrast, at OLR of 42.32gVS/Lreactor, the pH of effluent from the reactors with 0.4g/gVSFWadded of ZVI increased to 7.8-8.2, VFA/ALK decreased to <0.1, and the final CH4 yield was ∼380mL/gVSFWadded, suggesting inhibition of excessive acidification. After adding powdered or scrap metal ZVI to the acidogenic reactors, the fractional content of butyric acid changed from 30-40% to 0%, while, that of acetic acid increased. These results indicate that adding ZVI to FW digestion at high OLRs could eliminate excessive acidification by promoting butyric acid conversion and enhancing methanogen activity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Termination of nanoscale zero-valent iron reactivity by addition of bromate as a reducing reactivity competitor

NASA Astrophysics Data System (ADS)

Mines, Paul D.; Kaarsholm, Kamilla M. S.; Droumpali, Ariadni; Andersen, Henrik R.; Lee, Wontae; Hwang, Yuhoon

2017-09-01

Remediation of contaminated groundwater by nanoscale zero-valent iron (nZVI) is widely becoming a leading environmentally friendly solution throughout the globe. Since a wide range of various nZVI-containing materials have been developed for effective remediation, it is necessary to determine an appropriate way to terminate the reactivity of any nZVI-containing material for a practical experimental procedure. In this study, bimetallic Ni/Fe-NPs were prepared to enhance overall reduction kinetics owing to the catalytic reactivity of nickel on the surface of nZVI. We have tested several chemical strategies in order to terminate nZVI reactivity without altering the concentration of volatile compounds in the solution. The strategies include surface passivation in alkaline conditions by addition of carbonate, and consumption of nZVI by a reaction competitor. Four halogenated chemicals, trichloroethylene, 1,1,1-trichloroethane, atrazine, and 4-chlorophenol, were selected and tested as model groundwater contaminants. Addition of carbonate to passivate the nZVI surface was not effective for trichloroethylene. Nitrate and then bromate were applied to competitively consume nZVI by their faster reduction kinetics. Bromate proved to be more effective than nitrate, subsequently terminating nZVI reactivity for all four of the tested halogenated compounds. Furthermore, the suggested termination method using bromate was successfully applied to obtain trichloroethylene reduction kinetics. Herein, we report the simple and effective method to terminate the reactivity of nZVI by addition of a reducing reactivity competitor.

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron: Synergetic effect, efficiency optimization and mechanism.

PubMed

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

2017-02-01

In this study, a novel nanoscale zero-valent iron (nZVI) composite material was successfully synthesized using a low-cost natural clay, "Hangjin 2 # clay" (HJ clay) as the support and tested for the decolorization of the azo dye Methyl Orange (MO) in aqueous solution by nZVI particles. According to the characterization and MO decolorization experiments, the sample with 5:1 HJ clay-supported nZVI (HJ/nZVI) mass ratio (HJ-nZVI5) showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe 0 dosage, the HJ-nZVI1 and HJ-nZVI5 samples demonstrated a synergetic effect for the decolorization of MO: their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and nZVIs, or the sum of HJ clay and nZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the nZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-nZVI dosage, higher temperature and under N 2 atmosphere, while the MO initial concentration and pH were negatively correlated to the efficiency. HJ clay not only works as a carrier for nZVI nanoparticles, but also contributes to the decolorization through an "adsorption-enhanced reduction" mechanism. The high efficiency of HJ-nZVI for decontamination gives it great potential for use in a variety of remediation applications. Copyright © 2016. Published by Elsevier B.V.

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

PubMed

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

2012-02-01

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

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

PubMed

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

2013-10-21

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

Iron coated pottery granules for arsenic removal from drinking water.

PubMed

Dong, Liangjie; Zinin, Pavel V; Cowen, James P; Ming, Li Chung

2009-09-15

A new media, iron coated pottery granules (ICPG) has been developed for As removal from drinking water. ICPG is a solid phase media that produces a stable Fe-Si surface complex for arsenic adsorption. Scanning electron microscopy (SEM) was used to document the physical attributes (grain size, pore size and distribution, surface roughness) of the ICPG media. Several advantages of the ICPG media such as (a) its granular structure, (b) its ability to absorb As via the F(0) coating on the granules' surface; (c) the inexpensive preparation process for the media from clay material make ICPG media a highly effective media for removing arsenic at normal pH. A column filtration test demonstrated that within the stability region (flow rate lower than 15L/h, EBCT >3 min), the concentration of As in the influent was always lower than 50 microg/L. The 2-week system ability test showed that the media consistently removed arsenic from test water to below the 5 microg/L level. The average removal efficiencies for total arsenic, As(III), and As(V) for a 2-week test period were 98%, 97%, and 99%, respectively, at an average flow rate of 4.1L/h and normal pH. Measurements of the Freundlich and Langmuir isotherms at normal pH show that the Freundlich constants of the ICPG are very close to those of ferric hydroxide, nanoscale zero-valent iron and much higher than those of nanocrystalline titanium dioxide. The parameter 1/n is smaller than 0.55 indicating a favorable adsorption process [K. Hristovski, A. Baumgardner, P. Westerhoff, Selecting metal oxide nanomaterials for arsenic removal in fixed bed columns: from nanopowders to aggregated nanoparticle media, J. Hazard. Mater. 147 (2007) 265-274]. The maximum adsorption capacity (q(e)) of the ICPG from the Langmuir isotherm is very close to that of nanoscale zero-valent indicating that zero-valent iron is involved in the process of the As removal from the water. The results of the toxicity characteristic leaching procedure (TCLP

Superconducting FeSe0.1Te0.9 thin films integrated on Si-based substrates

NASA Astrophysics Data System (ADS)

Huang, Jijie; Chen, Li; Li, Leigang; Qi, Zhimin; Sun, Xing; Zhang, Xinghang; Wang, Haiyan

2018-05-01

With the goal of integrating superconducting iron chalcogenides with Si-based electronics, superconducting FeSe0.1Te0.9 thin films were directly deposited on Si and SiOx/Si substrates without any buffer layer by a pulsed laser deposition (PLD) method. Microstructural characterization showed excellent film quality with mostly c-axis growth on both types of substrates. Superconducting properties (such as superconducting transition temperature T c and upper critical field H c2) were measured to be comparable to that of the films on single crystal oxide substrates. The work demonstrates the feasibility of integrating superconducting iron chalcogenide (FeSe0.1Te0.9) thin films with Si-based microelectronics.

Degradation of 4-Chloro-3,5-Dimethylphenol by a Heterogeneous Fenton-Like Reaction Using Nanoscale Zero-Valent Iron Catalysts

PubMed Central

Xu, Lejin; Wang, Jianlong

2013-01-01

Abstract Degradation of 4-chloro-3,5-dimethylphenol (PCMX) by a heterogeneous Fenton-like process using nanoparticulate zero-valent iron (nZVI) and hydrogen peroxide (H2O2) at pH 6.3 was investigated. Interactive effects of three factors—initial PCMX concentration, nZVI dosage, and H2O2 concentration—were investigated using the response surface method based on the Box–Behnken design. Experimental results showed that complete decomposition of PCMX and 65% of total organic carbon removal were observed after 30 min of reaction at neutral pH under recommended reaction conditions: nZVI, 1.0 g/L; H2O2, 18 mM; and initial PCMX concentration, 0.15 g/L. Based on the effects of scavengers n-butanol and KI, removal of PCMX was mainly attributed to the attack of •OH, especially the surface-bonded •OH. A possible degradation pathway of PCMX was proposed. PMID:23781127

Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe 5O 6

DOE PAGES

Lavina, Barbara; Meng, Yue

2015-06-26

The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe 4O 5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe 3O 4, and Fe 2O 3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe 5O 6. The new compound, which has an orthorhombic structure, was obtained in themore » pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe 5O 6, Fe 4O 5, and h-Fe 3O 4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe 5O 6, along with FeO and Fe 4O 5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe 5O 6, Fe 4O 5, and h-Fe 3O 4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth’s mantle can be defined.« less

Magnetic characteristics of ultrafine Fe particles reduced from uniform iron oxide particles

NASA Astrophysics Data System (ADS)

Bridger, K.; Watts, J.; Tadros, M.; Xiao, Gang; Liou, S. H.; Chien, C. L.

1987-04-01

Uniform, cubic 0.05-μm iron oxide particles were formed by forced hydrolysis of ferric perchlorate. These particles were reduced to α-Fe by heating in hydrogen at temperatures between 300 and 500 °C. The effect of reduction temperature and various prereduction treatments on the microstructure of the iron particles will be discussed. Complete reduction to α-Fe was established by 57Fe Mössbauer spectroscopy and x-ray diffraction. Magnetic measurements on epoxy and polyurethane films containing these particles with various mass fractions gave coercivities as high as 1000 Oe. The relationship between the magnetic measurements and the microstructure will be discussed. Na2SiO3 is found to be the best coating material for the process of reducing iron oxide particles to iron.

Characterizing the discoloration of methylene blue in Fe0/H2O systems.

PubMed

Noubactep, C

2009-07-15

Methylene blue (MB) was used as a model molecule to characterize the aqueous reactivity of metallic iron in Fe(0)/H(2)O systems. Likely discoloration mechanisms under used experimental conditions are: (i) adsorption onto Fe(0) and Fe(0) corrosion products (CP), (ii) co-precipitation with in situ generated iron CP, (iii) reduction to colorless leukomethylene blue (LMB). MB mineralization (oxidation to CO(2)) is not expected. The kinetics of MB discoloration by Fe(0), Fe(2)O(3), Fe(3)O(4), MnO(2), and granular activated carbon were investigated in assay tubes under mechanically non-disturbed conditions. The evolution of MB discoloration was monitored spectrophotometrically. The effect of availability of CP, Fe(0) source, shaking rate, initial pH value, and chemical properties of the solution were studied. The results present evidence supporting co-precipitation of MB with in situ generated iron CP as main discoloration mechanism. Under high shaking intensities (>150 min(-1)), increased CP generation yields a brownish solution which disturbed MB determination, showing that a too high shear stress induced the suspension of in situ generated corrosion products. The present study clearly demonstrates that comparing results from various sources is difficult even when the results are achieved under seemingly similar conditions. The appeal for an unified experimental procedure for the investigation of processes in Fe(0)/H(2)O systems is reiterated.

Degradation of 1,2,3-trichloropropane (TCP): hydrolysis, elimination, and reduction by iron and zinc.

PubMed

Sarathy, Vaishnavi; Salter, Alexandra J; Nurmi, James T; O'Brien Johnson, Graham; Johnson, Richard L; Tratnyek, Paul G

2010-01-15

1,2,3-Trichloropropane (TCP) is an emerging contaminant because of increased recognition of its occurrence in groundwater, potential carcinogenicity, and resistance to natural attenuation. The physical and chemical properties of TCP make it difficult to remediate, with all conventional options being relatively slow or inefficient. Treatments that result in alkaline conditions (e.g., permeable reactive barriers containing zerovalent iron) favor base-catalyzed hydrolysis of TCP, but high temperature (e.g., conditions of in situ thermal remediation) is necessary for this reaction to be significant. Common reductants (sulfide, ferrous iron adsorbed to iron oxides, and most forms of construction-grade or nano-Fe(0)) produce insignificant rates of reductive dechlorination of TCP. Quantifiable rates of TCP reduction were obtained with several types of activated nano-Fe(0), but the surface area normalized rate contants (k(SA)) for these reactions were lower than is generally considered useful for in situ remediation applications (10(-4) L m(-2) h(-1)). Much faster rates of degradation of TCP were obtained with granular Zn(0), (k(SA) = 10(-3) - 10(-2) L m(-2) h(-1)) and potentially problematic dechlorination intermediates (1,2- or 1,3-dichloropropane, 3-chloro-1-propene) were not detected. The advantages of Zn(0) over Fe(0) are somewhat peculiar to TCP and may suggest a practical application for Zn(0) even though it has not found favor for remediation of contamination with other chlorinated solvents.

Polyvinylpyrrolidone and arsenic-induced changes in biological responses of model aquatic organisms exposed to iron-based nanoparticles

NASA Astrophysics Data System (ADS)

Llaneza, Verónica; Rodea-Palomares, Ismael; Zhou, Zuo; Rosal, Roberto; Fernández-Pina, Francisca; Bonzongo, Jean-Claude J.

2016-08-01

The efficiency of zero-valent iron particles used in the remediation of contaminated groundwater has, with the emergence of nanotechnology, stimulated interest on the use of nano-size particles to take advantage of high-specific surface area and reactivity characteristics of nanoparticles (NPs). Accordingly, engineered iron-NPs are among the most widely used nanomaterials for in situ remediation. However, while several ecotoxicity studies have been conducted to investigate the adverse impacts of these NPs on aquatic organisms, research on the implications of spent iron-based NPs is lacking. In this study, a comparative approach is used, in which the biological effects of three iron-based NPs (Fe3O4 and γ-Fe2O3 NPs with particle sizes ranging from 20 to 50 nm, and Fe0-NPs with an average particle size of 40 nm) on Raphidocelis subcapitata (formely known as Pseudokirchneriella subcapitata) and Daphnia magna were investigated using both as-prepared and pollutant-doped Fe-based NPs. For the latter, arsenic (As) was used as example sorbed pollutant. The results show that improved degree of NP dispersion by use of polyvinylpyrrolidone overlapped with both increased arsenic adsorption capacity and toxicity to the tested organisms. For R. subcapitata, Fe-oxide NPs were more toxic than Fe0-NPs, due primarily to differences in the degree of NPs aggregation and ability to produce reactive oxygen species. For the invertebrate D. magna, a similar trend of biological responses was observed, except that sorption of As to Fe0-NPs significantly increased the toxic response when compared to R. subcapitata. Overall, these findings point to the need for research on downstream implications of NP-pollutant complexes generated during water treatment by injection of NPs into aquatic systems.

Magnetic moment arrangement in amorphous Fe 0.66Er 0.19B 0.15

NASA Astrophysics Data System (ADS)

Szymański, K.; Kalska, B.; Satuła, D.; Dobrzyński, L.; Broddefalk, A.; Wäppling, R.; Nordblad, P.

2002-11-01

Magnetization measurements and Mössbauer spectroscopy with and without a monochromatic circularly polarized Mössbauer source (MCPMS) have been performed in order to determine the magnetic properties of the amorphous alloy Fe 0.66Er 0.19B 0.15. The system is found to order ferrimagnetically at TC=330 K and to show a compensation temperature ( Tcomp) at 120 K. A reorientation of the magnetic moments of iron and erbium during sample cooling through the compensation point in magnetic field is clearly displayed in the MCPMS data. The orientation of the net magnetic moment is due to the orientation of Fe moments above Tcomp and to Er moments at low temperatures. The results are compatible with a model of predominantly antiferromagnetic Fe-Er coupling accompanied by random local anisotropy acting on the Er moments.

Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

NASA Technical Reports Server (NTRS)

Jeanloz, Raymond; O'Neill, Bridget; Pasternak, Moshe P.; Taylor, R. D.; Bohlen, Steven R.

1992-01-01

Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

Zero-valent iron treatment of dark brown colored coffee effluent: Contributions of a core-shell structure to pollutant removals.

PubMed

Tomizawa, Mayuka; Kurosu, Shunji; Kobayashi, Maki; Kawase, Yoshinori

2016-12-01

The decolorization and total organic carbon (TOC) removal of dark brown colored coffee effluent by zero-valent iron (ZVI) have been systematically examined with solution pH of 3.0, 4.0, 6.0 and 8.0 under oxic and anoxic conditions. The optimal decolorization and TOC removal were obtained at pH 8.0 with oxic condition. The maximum efficiencies of decolorization and TOC removal were 92.6 and 60.2%, respectively. ZVI presented potential properties for pollutant removal at nearly neutral pH because of its core-shell structure in which shell or iron oxide/hydroxide layer on ZVI surface dominated the decolorization and TOC removal of coffee effluent. To elucidate the contribution of the core-shell structure to removals of color and TOC at the optimal condition, the characterization of ZVI surface by scanning electron microscopy (SEM) with an energy dispersive X-ray spectroscope (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) was conducted. It was confirmed that the core-shell structure was formed and the shell on ZVI particulate surface and the precipitates formed during the course of ZVI treatment consisted of iron oxides and hydroxides. They were significantly responsible for decolorization and TOC removal of coffee effluent via adsorption to shell on ZVI surface and inclusion into the precipitates rather than the oxidative degradation by OH radicals and the reduction by emitted electrons. The presence of dissolved oxygen (DO) enhanced the formation of the core-shell structure and as a result improved the efficiency of ZVI treatment for the removal of colored components in coffee effluents. ZVI was found to be an efficient material toward the treatment of coffee effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic transformation of persistent contaminants using a new composite material based on nanosized zero-valent iron.

PubMed

Dror, Ishai; Jacov, Osnat Merom; Cortis, Andrea; Berkowitz, Brian

2012-07-25

A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions.

CHEMICAL INTERACTIONS OF ARSENATE, ARSENITE, PHOSPHATE, AND SILICATE WITH IRON (II, III) HYDROXYCARBONATE GREEN RUST

EPA Science Inventory

Granular zerovalent iron has been proposed to be used as a medium in permeable reactive barriers (PRBs) to remove arsenic from contaminated groundwater. Iron(II, III) hydroxycarbonate green rust (carbonate green rust, or CGR) is a major corrosion product of zerovalent iron under ...

CHEMICAL INTERACTIONS OF ARSENATE, ARSENITE, PHOSPHATE, AND SILICATE WITH IRON (II,III) HYDROXYCARBONATE GREEN RUST

EPA Science Inventory

Granular zerovalent iron has been proposed to be used as a medium in permeable reactive barriers (PRBs) to remove arsenic from contaminated groundwater. Iron(II, III) hydroxycarbonate green rust (carbonate green rust, or CGR) is a major corrosion product of zerovalent iron under ...

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

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Metal(loid)s behaviour in soils amended with nano zero-valent iron as a function of pH and time.

PubMed

Vítková, Martina; Rákosová, Simona; Michálková, Zuzana; Komárek, Michael

2017-01-15

Nano zero-valent iron (nZVI) is currently investigated as a stabilising amendment for contaminated soils. The effect of pH (4-8) and time (48 and 192 h) on the behaviour of nZVI-treated Pb-Zn and As-contaminated soil samples was assessed. Additionally, soil leachates were subsequently used to study the direct interaction between soil solution components and nZVI particles in terms of mineralogical changes and contaminant retention. A typical U-shaped leaching trend as a function of pH was observed for Cd, Pb and Zn, while As was released predominantly under alkaline conditions. Oxidising conditions prevailed, so pH was the key controlling parameter rather than redox conditions. Generally, longer contact time resulted in increased soluble concentrations of metal(loid)s. However, the stabilisation effect of nZVI was only observed after the direct soil leachate-nZVI interactions, showing enhanced redox and sorption processes for the studied metals. A significant decrease of dissolved As concentrations was observed for both experimental soils, but with different efficiencies depending on neutralisation capacity, organic matter content or solid fractionation of As related to the origin of the soils. Scorodite (FeAsO 4 ·2H 2 O) was predicted as a potential solubility-controlling mineral phase for As. Sorption of metal(loid)s onto secondary Fe- and Al-(oxyhydr)oxides (predicted to precipitate at pH > 5) represents an important scavenger mechanism. Moreover, transmission electron microscopy confirmed the retention of Zn and Pb under near-neutral and alkaline conditions by newly formed Fe oxides or aluminosilicates. This study shows that the efficiency of nZVI application strongly depends not only on soil pH-Eh conditions and contaminant type, but also on the presence of organic matter and other compounds such as Al/Fe/Mn oxyhydroxides and clay minerals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Iron Corrosion Observations: Pu(VI)-Fe Reduction Studies

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

Reed, Donald T.; Swanson, Juliet S.; Richmann, Michael K.

Iron and Pu Reduction: (1) Very different appearances in iron reaction products were noted depending on pH, brine and initial iron phase; (2) Plutonium was associated with the Fe phases; (3) Green rust was often noted at the higher pH; (4) XANES established the green rust to be an Fe2/3 phase with a bromide center; and (5) This green rust phase was linked to Pu as Pu(IV).

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

Transport of carboxymethyl cellulose-coated zerovalent iron nanoparticles in a sand tank: Effects of sand grain size, nanoparticle concentration and injection velocity.

PubMed

Li, Jing; Rajajayavel, Sai Rajasekar C; Ghoshal, Subhasis

2016-05-01

The transport of nanoscale zerovalent iron (NZVI) particles colloidally stabilized with 70,000 Da carboxymethyl cellulose (CMC), through sands with mean grain diameters of 180, 340 and 1140 μm (referred to as fine, intermediate and coarse-sized sand, respectively) was investigated in a 70-cm long, two-dimensional tank. The effect of NZVI concentrations (1 and 3 g-Fe L(-1)) and CMC concentrations (1 and 2 g L(-1)) and injection velocities (0.96 and 0.40 cm min(-1)) on particle transport were also evaluated with the intermediate sand. The overall NZVI mass fractions eluted from the tank were 36%, 25% and 16% in the coarse, intermediate and fine sands, respectively, when injected with 1 g L(-1) NZVI stabilized in 1 g L(-1) CMC. However, the mass fraction eluted reduced to 2.33% when the injection velocity was reduced from 0.96 to 0.40 cm min(-1) in the intermediate-sized sand. Maximum transport efficiency (38% NZVI mass eluted) in the intermediate-sized sand was achieved with 3 g L(-1) NZVI suspended in 2 g L(-1) CMC at an injection velocity of 0.96 cm min(-1). The transport efficiency was substantially decreased (11% NZVI mass eluted) when 3 g L(-1) NZVI was stabilized with only 1 g L(-1) CMC. The NZVI mean particle diameters in the porewaters remained unchanged at different locations in the tank suggesting that straining or gravity settling did not influence NZVI deposition. After NZVI injection, the hydraulic conductivity in the tank reduced by 80%-96%, depending on the CMC concentration and injection velocity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dual element (CCl) isotope approach to distinguish abiotic reactions of chlorinated methanes by Fe(0) and by Fe(II) on iron minerals at neutral and alkaline pH.

PubMed

Rodríguez-Fernández, Diana; Heckel, Benjamin; Torrentó, Clara; Meyer, Armin; Elsner, Martin; Hunkeler, Daniel; Soler, Albert; Rosell, Mònica; Domènech, Cristina

2018-05-07

A dual element CCl isotopic study was performed for assessing chlorinated methanes (CMs) abiotic transformation reactions mediated by iron minerals and Fe(0) to further distinguish them in natural attenuation monitoring or when applying remediation strategies in polluted sites. Isotope fractionation was investigated during carbon tetrachloride (CT) and chloroform (CF) degradation in anoxic batch experiments with Fe(0), with FeCl 2 (aq), and with Fe-bearing minerals (magnetite, Mag and pyrite, Py) amended with FeCl 2 (aq), at two different pH values (7 and 12) representative of field and remediation conditions. At pH 7, only CT batches with Fe(0) and Py underwent degradation and CF accumulation evidenced hydrogenolysis. With Py, thiolytic reduction was revealed by CS 2 yield and is a likely reason for different Λ value (Δδ 13 C/Δδ 37 Cl) comparing with Fe(0) experiments at pH 7 (2.9 ± 0.5 and 6.1 ± 0.5, respectively). At pH 12, all CT experiments showed degradation to CF, again with significant differences in Λ values between Fe(0) (5.8 ± 0.4) and Fe-bearing minerals (Mag, 2 ± 1, and Py, 3.7 ± 0.9), probably evidencing other parallel pathways (hydrolytic and thiolytic reduction). Variation of pH did not significantly affect the Λ values of CT degradation by Fe(0) nor Py. CF degradation by Fe(0) at pH 12 showed a Λ (8 ± 1) similar to that reported at pH 7 (8 ± 2), suggesting CF hydrogenolysis as the main reaction and that CF alkaline hydrolysis (13.0 ± 0.8) was negligible. Our data establish a base for discerning the predominant or combined pathways of CMs natural attenuation or for assessing the effectiveness of remediation strategies using recycled minerals or Fe(0). Copyright © 2018 Elsevier Ltd. All rights reserved.

Antimicrobial and Genotoxicity Effects of Zero-valent Iron Nanoparticles

PubMed Central

Barzan, Elham; Mehrabian, Sedigheh; Irian, Saeed

2014-01-01

Background: In a world of nanotechnology, the first concern is the potential environmental impact of nanoparticles. An efficient way to estimate nanotoxicity is to monitor the responses of bacteria exposed to these particles. Objectives: The current study explored the antimicrobial properties of nZVI (zero-valent Iron nanoparticles) on the Gram-negative bacterial systems Erwinia amylovora, Xanthomonas oryzae and the Gram-positive bacterial systems Bacillus cereus and Streptomyces spp. The genotoxicity potential of nZVI was also assayed. Materials and Methods: The toxicity of nZVI was tested by two different methods: Growing bacteria in liquid (broth dilution) and agar media (challenge test) containing different nZVI concentrations for 24-72 hours. The genotoxicity of nZVI was assessed using the preincubation version of the Ames test. Results: The lowest concentrations of nZVI that inhibited the visible growth (MIC) of E. amylovora, X. oryzae, B. cereus and Streptomyces spp. were 625, 550, 1250 and 1280 ppm, respectively. The minimum bactericidal concentration (MBC) for E. amylovora and X. oryzae were 10,000 and 5,000 ppm of nZVI, respectively. MBC was not observed for the Gram positive bacteria. No bacteriostatic and bactericidal effects were observed for oxidized nZVI. Mutant frequency did not increase according to the vehicle control at the concentrations assayed, indicating a lack of mutagenicity associated with nZVI. Conclusions: nZVI nanoparticles are not mutagenic at low concentrations, therefore they can be used without detrimental effects on soil bacteria. PMID:25147712

Microbial mediated iron redox cycling in Fe (hydr)oxides for nitrite removal.

PubMed

Lu, Yongsheng; Xu, Lu; Shu, Weikang; Zhou, Jizhi; Chen, Xueping; Xu, Yunfeng; Qian, Guangren

2017-01-01

Nitrite, at an environmentally relevant concentration, was significantly reduced with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. The average nitrite removal rates of 1.28±0.08 and 0.65±0.02(mgL -1 )h -1 were achieved with ferrihydrite and magnetite, respectively. The results showed that nitrite removal was able to undergo multiple redox cycles with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. During the bioreduction of the following cycles, biogenic Fe(II) was subsequently chemically oxidized to Fe(III), which is associated with nitrite reduction. There was 11.18±1.26mgL -1 of NH 4 + -N generated in the process of redox cycling of ferrihydrite. Additionally, results obtained by using X-ray diffraction showed that ferrihydrite and magnetite remained mainly stable in the system. This study indicated that redox cycling of Fe in iron (hydr)oxides was a potential process associated with NO 2 - -N removal from solution, and reduced most nitrite abiotically to gaseous nitrogen species. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]-: formation pathway of dinitrosyl iron complexes (DNICs) from nitrosylation of biomimetic rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et).

PubMed

Lu, Tsai-Te; Chiou, Show-Jen; Chen, Chun-Yu; Liaw, Wen-Feng

2006-10-16

Nitrosylation of the biomimetic reduced- and oxidized-form rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et) in a 1:1 stoichiometry led to the formation of the extremely air- and light-sensitive mononitrosyl tris(thiolate) iron complexes (MNICs) [Fe(NO)(SR)3]- along with byproducts [SR]- or (RS)2. Transformation of [Fe(NO)(SR)3]- into dinitrosyl iron complexes (DNICs) [(RS)2Fe(NO)2]- and Roussin's red ester [Fe2(mu-SR)2(NO)4] occurs rapidly under addition of 1 equiv of NO(g) and [NO]+, respectively. Obviously, the mononitrosyl tris(thiolate) complex [Fe(NO)(SR)3]- acts as an intermediate when the biomimetic oxidized- and reduced-form rubredoxin [Fe(SR)4]2-/1- exposed to NO(g) were modified to form dinitrosyl iron complexes [(RS)2Fe(NO)2]-. Presumably, NO binding to the electron-deficient [Fe(III)(SR)4]- and [Fe(III)(NO)(SR)3]- complexes triggers reductive elimination of dialkyl/diphenyl disulfide, while binding of NO radical to the reduced-form [Fe(II)(SR)4]2- induces the thiolate-ligand elimination. Protonation of [Fe(NO)(SEt)3]- yielding [Fe(NO)(SPh)3]- by adding 3 equiv of thiophenol and transformation of [Fe(NO)(SPh)3]- to [Fe(NO)(SEt)3]- in the presence of 3 equiv of [SEt]-, respectively, demonstrated that complexes [Fe(NO)(SPh)3]- and [Fe(NO)(SEt)3]- are chemically interconvertible. Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]- were isolated and characterized by X-ray diffraction. The mean NO bond distances of 1.181(7) A (or 1.191(7) A) in complex [(EtS)2Fe(NO)2]- are nearly at the upper end of the 1.178(3)-1.160(6) A for the anionic {Fe(NO)2}9 DNICs, while the mean FeN(O) distances of 1.674(6) A (or 1.679(6) A) exactly fall in the range of 1.695(3)-1.661(4) A for the anionic {Fe(NO)2}9 DNICs.

Chemical synthesis of battery grade super-iron barium and potassium Fe(VI) ferrate compounds

NASA Astrophysics Data System (ADS)

Licht, Stuart; Naschitz, Vera; Liu, Bing; Ghosh, Susanta; Halperin, Nadezhda; Halperin, Leonid; Rozen, Dmitri

The chemical preparation of high purity potassium and barium ferrates for alkaline electrochemical storage are presented. The synthesized salts are used to demonstrate a variety of high capacity super-iron (Zn anode) alkaline AAA cell configurations which utilize these Fe(V) salts. Results of 500 days, full stability, of the synthesized K 2FeO 4 are presented. Synthetic pathways yielding 80-100 g of 96.5-99.5% pure K 2FeO 4 and BaFeO 4 are presented, and the products of these syntheses are demonstrated to provide a high energy electrochemical discharge in a variety of AAA alkaline cells. BaFeO 4 super-iron alkaline AAA cells provide over 0.8 W h during 2.8 Ω discharge, yielding over 200% higher capacity than conventional alkaline batteries. The barium super-iron cell configurations studied provide higher capacity than the potassium super-iron alkaline cell configurations studied.

Enhanced degradation of 4-nitrophenol by microwave assisted Fe/EDTA process.

PubMed

Liu, Bo; Li, Song; Zhao, Yongjun; Wu, Wenfei; Zhang, Xuxiang; Gu, Xueyuan; Li, Ruihua; Yang, Shaogui

2010-04-15

A microwave assisted zero-valent iron oxidation process was studied in order to investigate the synergetic effects of MW irradiation on Fe/EDTA system (Fe/EDTA/MW) treated 4-nitrophenol (4-NP) from aqueous solution. The results indicated that the thermal effect of microwave improved the removal effect of 4-NP and TOC through raising the temperature of the system, as well as the non-thermal effect generated by the interaction between the microwave and the Fe resulting in an increase in the hydrophobic character of Fe surface. During the degradation of 4-NP in Fe/EDTA/MW system, the optimum value for MW power, Fe, EDTA dosage was 400 W, 2 g and 0.4 mM, respectively. The possible pathway for degrading the 4-NP was proposed based on GC/MS and HPLC analysis of the degradation intermediates. The concentration change course of the main bio-refractory by-products, the aminophenol formed in the degradation of 4-NP suggested a more efficient degradation and mineralization in Fe/EDTA/MW system. Finally, BOD(5)/COD(Cr) of the solution increased from 0.237 to 0.635 after reaction for 18 min, indicating that the biodegradability of wastewater was greatly improved by Fe/EDTA/MW system and would benefit to further treatment by biochemical methods. Crown Copyright 2009. Published by Elsevier B.V. All rights reserved.

High purity Fe3O4 from Local Iron Sand Extraction

NASA Astrophysics Data System (ADS)

Gunanto, Y. E.; Izaak, M. P.; Jobiliong, E.; Cahyadi, L.; Adi, W. A.

2018-04-01

Indonesia has a long coastline and is rich with iron sand. The iron sand is generally rich in various elements such as iron and titanium. One of the products processing of the iron sand mineral is iron (II) (III) oxide (magnetite Fe3O4). The stages of purification process to extracting magnetite phase and discarding the other phases has been performed. Magnetite phase analysis of ironsand extraction retrieved from Indonesia have been investigated. The result of analysis element of iron sand shows that it consists of majority Fe around 65 wt%. However, there are still 17 impurities such as Ti, Al, Ce, Co, Cr, Eu, La, Mg, Mn, Na, Sc, Sm, Th, V, Yb, and Zn. After extraction process, Fe element content increases up to 94%. The iron sand powder after milling for 10 hours and separating using a magnetic separator, the iron sand powders are dissolved in acid chloride solution to form a solution of iron chloride, and this solution is sprinkled with sodium hydroxide to obtain fine powders of Fe3O4. The fine powders which formed were washed with de-mineralization water. The X-ray diffraction pattern shows that the fine powders have a single phase of Fe3O4. The analysis result shows that the sample has the chemical formula: Fe3O4 with a cubic crystal system, space group: Fd-3m and lattice parameters: a = b = c = 8.3681 (1) Å, α = β = γ = 90°. The microstructure analysis shows that the particle of Fe3O4 homogeneously shaped like spherical. The magnetic properties using vibrating sample magnetometer shows that Fe3O4 obtained have ferromagnetic behavior with soft magnetic characteristics. We concluded that this purification of iron sand had been successfully performed to obtain fine powders of Fe3O4 with high purity.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Pressure-controlled injection of guar gum stabilized microscale zerovalent iron for groundwater remediation.

PubMed

Luna, M; Gastone, F; Tosco, T; Sethi, R; Velimirovic, M; Gemoets, J; Muyshondt, R; Sapion, H; Klaas, N; Bastiaens, L

2015-10-01

The paper reports a pilot injection test of microsized zerovalent iron (mZVI) dispersed in a guar gum shear thinning solution. The test was performed in the framework of the EU research project AQUAREHAB in a site in Belgium contaminated by chlorinated aliphatic hydrocarbons (CAHs). The field application was aimed to overcome those critical aspects which hinder mZVI field injection, mainly due to the colloidal instability of ZVI-based suspensions. The iron slurry properties (iron particles size and concentration, polymeric stabilizer type and concentration, slurry viscosity) were designed in the laboratory based on several tests (reactivity tests towards contaminants, sedimentation tests and rheological measurements). The particles were delivered into the aquifer through an injection well specifically designed for controlled-pressure delivery (approximately 10 bars). The well characteristics and the critical pressure of the aquifer (i.e. the injection pressure above which fracturing occurs) were assessed via two innovative injection step rate tests, one performed with water and the other one with guar gum. Based on laboratory and field preliminary tests, a flow regime at the threshold between permeation and preferential flow was selected for mZVI delivery, as a compromise between the desired homogeneous distribution of the mZVI around the injection point (ensured by permeation flow) and the fast and effective injection of the slurry (guaranteed by high discharge rates and injection pressure, resulting in the generation of preferential flow paths). A monitoring setup was designed and installed for the real-time monitoring of relevant parameters during injection, and for a fast determination of the spatial mZVI distribution after injection via non-invasive magnetic susceptibility measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Biphasic reduction model for predicting the impacts of dye-bath constituents on the reduction of tris-azo dye Direct Green-1 by zero valent iron (Fe0).

PubMed

Kumar, Raja; Sinha, Alok

2017-02-01

Influence of common dye-bath additives, namely sodium chloride, ammonium sulphate, urea, acetic acid and citric acid, on the reductive decolouration of Direct Green 1 dye in the presence of Fe 0 was investigated. Organic acids improved dye reduction by augmenting Fe 0 corrosion, with acetic acid performing better than citric acid. NaCl enhanced the reduction rate by its 'salting out' effect on the bulk solution and by Cl - anion-mediated pitting corrosion of iron surface. (NH 4 ) 2 SO 4 induced 'salting out' effect accompanied by enhanced iron corrosion by SO 4 2- anion and buffering effect of NH 4 + improved the reduction rates. However, at 2g/L (NH 4 ) 2 SO 4 concentration, complexating of SO 4 2- with iron oxides decreased Fe 0 reactivity. Urea severely compromised the reduction reaction, onus to its chaotropic and 'salting in' effect in solution, and due to it masking the Fe 0 surface. Decolouration obeyed biphasic reduction kinetics (R 2 >0.993 in all the cases) exhibiting an initial rapid phase, when more than 95% dye reduction was observed, preceding a tedious phase. Maximum rapid phase reduction rate of 0.955/min was observed at pH2 in the co-presence of all dye-bath constituents. The developed biphasic model reckoned the influence of each dye-bath additive on decolouration and simulated well with the experimental data obtained at pH2. Copyright © 2016. Published by Elsevier B.V.

Soybean Fe-S cluster biosynthesis regulated by external iron or phosphate fluctuation.

PubMed

Qin, Lu; Wang, Meihuan; Chen, Liyu; Liang, Xuejiao; Wu, Zhigeng; Lin, Zhihao; Zuo, Jia; Feng, Xiangyang; Zhao, Jing; Liao, Hong; Ye, Hong

2015-03-01

Iron and phosphorus are essential for soybean nodulation. Our results suggested that the deficiency of Fe or P impairs nodulation by affecting the assembly of functional iron-sulfur cluster via different mechanisms. Iron (Fe) and phosphorus (P) are important mineral nutrients for soybean and are indispensable for nodulation. However, it remains elusive how the pathways of Fe metabolism respond to the fluctuation of external Fe or P. Iron is required for the iron-sulfur (Fe-S) cluster assembly in higher plant. Here, we investigated the expression pattern of Fe-S cluster biosynthesis genes in the nodulated soybean. Soybean genome encodes 42 putative Fe-S cluster biosynthesis genes, which were expressed differently in shoots and roots, suggesting of physiological relevance. Nodules initiated from roots of soybean after rhizobia inoculation. In comparison with that in shoots, iron concentration was three times higher in nodules. The Fe-S cluster biosynthesis genes were activated and several Fe-S protein activities were increased in nodules, indicating that a more effective Fe-S cluster biosynthesis is accompanied by nodulation. Fe-S cluster biosynthesis genes were massively repressed and some Fe-S protein activities were decreased in nodules by Fe deficiency, leading to tiny nodules. Notably, P deficiency induced a similar Fe-deficiency response in nodules, i.e, certain Fe-S enzyme activity loss and tiny nodules. However, distinct from Fe-deficient nodules, higher iron concentration was accumulated and the Fe-S cluster biosynthesis genes were not suppressed in the P-deficiency-treated nodules. Taken together, our results showed that both Fe deficiency and P deficiency impair nodulation, but they affect the assembly of Fe-S cluster maybe via different mechanisms. The data also suggested that Fe-S cluster biosynthesis likely links Fe metabolism and P metabolism in root and nodule cells of soybean.

A mixed iron-manganese based pyrophosphate cathode, Na2Fe0.5Mn0.5P2O7, for rechargeable sodium ion batteries.

PubMed

Shakoor, Rana A; Park, Chan Sun; Raja, Arsalan A; Shin, Jaeho; Kahraman, Ramazan

2016-02-07

The development of secondary batteries based on abundant and cheap elements is vital. Among various alternatives to conventional lithium-ion batteries, sodium-ion batteries (SIBs) are promising due to the abundant resources and low cost of sodium. While there are many challenges associated with the SIB system, cathode is an important factor in determining the electrochemical performance of this battery system. Accordingly, ongoing research in the field of SIBs is inclined towards the development of safe, cost effective cathode materials having improved performance. In particular, pyrophosphate cathodes have recently demonstrated decent electrochemical performance and thermal stability. Herein, we report the synthesis, electrochemical properties, and thermal behavior of a novel Na2Fe0.5Mn0.5P2O7 cathode for SIBs. The material was synthesized through a solid state process. The structural analysis reveals that the mixed substitution of manganese and iron has resulted in a triclinic crystal structure (P1[combining macron] space group). Galvanostatic charge/discharge measurements indicate that Na2Fe0.5Mn0.5P2O7 is electrochemically active with a reversible capacity of ∼80 mA h g(-1) at a C/20 rate with an average redox potential of 3.2 V. (vs. Na/Na(+)). It is noticed that 84% of initial capacity is preserved over 90 cycles showing promising cyclability. It is also noticed that the rate capability of Na2Fe0.5Mn0.5P2O7 is better than Na2MnP2O7. Ex situ and CV analyses indicate that Na2Fe0.5Mn0.5P2O7 undergoes a single phase reaction rather than a biphasic reaction due to different Na coordination environment and different Na site occupancy when compared to other pyrophosphate materials (Na2FeP2O7 and Na2MnP2O7). Thermogravimetric analysis (25-550 °C) confirms good thermal stability of Na2Fe0.5Mn0.5P2O7 with only 2% weight loss. Owing to promising electrochemical properties and decent thermal stability, Na2Fe0.5Mn0.5P2O7, can be an attractive cathode for SIBs.

Ferritin contains less iron (59Fe) in cells when the protein pores are unfolded by mutation.

PubMed

Hasan, Mohammad R; Tosha, Takehiko; Theil, Elizabeth C

2008-11-14

Ferric minerals in ferritins are protected from cytoplasmic reductants and Fe2+ release by the protein nanocage until iron need is signaled. Deletion of ferritin genes is lethal; two critical ferritin functions are concentrating iron and oxidant protection (consuming cytoplasmic iron and oxygen in the mineral). In solution, opening/closing (gating) of eight ferritin protein pores controls reactions between external reductant and the ferritin mineral; pore gating is altered by mutation, low heat, and physiological urea (1 mm) and monitored by CD spectroscopy, protein crystallography, and Fe2+ release rates. To study the effects of a ferritin pore gating mutation in living cells, we cloned/expressed human ferritin H and H L138P, homologous to the frog open pore model that was unexpressable in human cells. Human ferritin H L138P behaved like the open pore ferritin model in vitro as follows: (i) normal protein cage assembly and mineralization, (ii) increased iron release (t1/2) decreased 17-fold), and (iii) decreased alpha-helix (8%). Overexpression (> 4-fold), in HeLa cells, showed for ferritin H L138P equal protein expression and total cell 59Fe but increased chelatable iron, 16%, p < 0.01 (59Fe in the deferoxamine-containing medium), and decreased 59Fe in ferritin, 28%, p < 0.01, compared with wild type. The coincidence of decreased 59Fe in open pore ferritin with increased chelatable 59Fe in cells expressing the ferritin open pore mutation suggests that ferritin pore gating influences to the amount of iron (59Fe) in ferritin in vivo.

Studies on the optimum conditions using acid-washed zero-valent iron/aluminum mixtures in permeable reactive barriers for the removal of different heavy metal ions from wastewater.

PubMed

Han, Weijiang; Fu, Fenglian; Cheng, Zihang; Tang, Bing; Wu, Shijiao

2016-01-25

The method of permeable reactive barriers (PRBs) is considered as one of the most practicable approaches in treating heavy metals contaminated surface and groundwater. The mixture of acid-washed zero-valent iron (ZVI) and zero-valent aluminum (ZVAl) as reactive medium in PRBs to treat heavy metal wastewater containing Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+) was investigated. The performance of column filled with the mixture of acid-washed ZVI and ZVAl was much better than the column filled with ZVI or ZVAl alone. At initial pH 5.4 and flow rates of 1.0 mL/min, the time that the removal efficiencies of Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+) were all above 99.5% can keep about 300 h using 80 g/40 g acid-washed ZVI/ZVAl when treating wastewater containing each heavy metal ions (Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+)) concentration of 20.0 mg/L. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize ZVI/ZVAl before and after reaction and the reaction mechanism of the heavy metal ions with ZVI/ZVAl was discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Evaluating the mobility of polymer-stabilised zero-valent iron nanoparticles and their potential to co-transport contaminants in intact soil cores.

PubMed

Chekli, L; Brunetti, G; Marzouk, E R; Maoz-Shen, A; Smith, E; Naidu, R; Shon, H K; Lombi, E; Donner, E

2016-09-01

The use of zero-valent iron nanoparticles (nZVI) has been advocated for the remediation of both soils and groundwater. A key parameter affecting nZVI remediation efficacy is the mobility of the particles as this influences the reaction zone where remediation can occur. However, by engineering nZVI particles with increased stability and mobility we may also inadvertently facilitate nZVI-mediated contaminant transport away from the zone of treatment. Previous nZVI mobility studies have often been limited to model systems as the presence of background Fe makes detection and tracking of nZVI in real systems difficult. We overcame this problem by synthesising Fe-59 radiolabelled nZVI. This enabled us to detect and quantify the leaching of nZVI-derived Fe-59 in intact soil cores, including a soil contaminated by Chromated-Copper-Arsenate. Mobility of a commercially available nZVI was also tested. The results showed limited mobility of both nanomaterials; <1% of the injected mass was eluted from the columns and most of the radiolabelled nZVI remained in the surface soil layers (the primary treatment zone in this contaminated soil). Nevertheless, the observed breakthrough of contaminants and nZVI occurred simultaneously, indicating that although the quantity transported was low in this case, nZVI does have the potential to co-transport contaminants. These results show that direct injection of nZVI into the surface layers of contaminated soils may be a viable remediation option for soils such as this one, in which the mobility of nZVI below the injection/remediation zone was very limited. This Fe-59 experimental approach can be further extended to test nZVI transport in a wider range of contaminated soil types and textures and using different application methods and rates. The resulting database could then be used to develop and validate modelling of nZVI-facilitated contaminant transport on an individual soil basis suitable for site specific risk assessment prior to n

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

PubMed

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

2018-06-01

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

Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation.

PubMed

Thomas, J Mathew; Hernandez, Rafael; Kuo, Chiang-Hai

2008-06-30

Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NACs contaminated waters. The process consists of the combination of zero-valent iron and an ozonation based treatment technique. Corrosion promoters are added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluene (DNT) was treated with the integrated process using a recirculated batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhances the reduction of 2,4-DNT with zero-valent iron. The addition of corrosion promoters resulted in 62% decrease in 2,4-DNT concentration to 2,4-diaminotoluene. The data shows that iron reduced the 2,4-DNT and ozone oxidized these products resulting in a 73% removal of TOC and a 96% decrease in 2,4-DNT concentration.

Superconductivity across Lifshitz transition and anomalous insulating state in surface K-dosed (Li0.8Fe0.2OH)FeSe.

PubMed

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-07-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity ( T c of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li 0.8 Fe 0.2 OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level ( E F ), can be continuously tuned to cross E F and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors.

Superconductivity across Lifshitz transition and anomalous insulating state in surface K–dosed (Li0.8Fe0.2OH)FeSe

PubMed Central

Ren, Mingqiang; Yan, Yajun; Niu, Xiaohai; Tao, Ran; Hu, Die; Peng, Rui; Xie, Binping; Zhao, Jun; Zhang, Tong; Feng, Dong-Lai

2017-01-01

In iron-based superconductors, understanding the relation between superconductivity and electronic structure upon doping is crucial for exploring the pairing mechanism. Recently, it was found that, in iron selenide (FeSe), enhanced superconductivity (Tc of more than 40 K) can be achieved via electron doping, with the Fermi surface only comprising M-centered electron pockets. By using surface K dosing, scanning tunneling microscopy/spectroscopy, and angle-resolved photoemission spectroscopy, we studied the electronic structure and superconductivity of (Li0.8Fe0.2OH)FeSe in the deep electron-doped regime. We find that a Γ-centered electron band, which originally lies above the Fermi level (EF), can be continuously tuned to cross EF and contribute a new electron pocket at Γ. When this Lifshitz transition occurs, the superconductivity in the M-centered electron pocket is slightly suppressed, and a possible superconducting gap with a small size (up to ~5 meV) and a dome-like doping dependence is observed on the new Γ electron pocket. Upon further K dosing, the system eventually evolves into an insulating state. Our findings provide new clues to understand superconductivity versus Fermi surface topology and the correlation effect in FeSe-based superconductors. PMID:28740865

Transport characteristics of nanoscale zero-valent iron carried by three different "vehicles" in porous media.

PubMed

Su, Yan; Zhao, Yong S; Li, Lu L; Qin, Chuan Y; Wu, Fan; Geng, Nan N; Lei, Jian S

2014-01-01

This study investigated the transport properties of nanoscale zero-valent iron (Fe(0)) (nZVI) carried by three vehicles: water, sodium dodecyl sulfate (SDS) solution, and SDS foam. Batch experiments were conducted to assess the sedimentation capability of nZVI particles in these three vehicles. Column experiments were conducted to investigate the transport properties of nZVI in porous media formed with different sizes of sand (0.25 mm to 0.5 mm, 0.5 mm to 0.9 mm, and 0.9 mm to 1.4 mm). Three main results were obtained. First, the batch experiments revealed that the stabilities of nZVI particles in SDS solution and SDS foam were improved, compared with that of nZVI particles in water. Moreover, the sedimentation of nZVI in foam was closely associated with the foam drainage volume. The nZVI content in foam was similar to that in the original foaming suspension, and the nZVI particle distribution in foam became significantly more uniform at a stirring speed of 3000 r/min. Second, the transport of nZVI was enhanced by foam compared with water and SDS solution for 0.25 mm to 0.5 mm diameter sand. For sand with diameters of 0.5 mm to 0.9 mm and 0.9 mm to 1.4 mm, the mobility of nZVI carried by SDS solution was optimal, followed by that of nZVI carried by foam and water. Thus, the mobility of nZVI in finer sand was significantly enhanced by foam, compared with that in coarse sand. In contrast, compared with the bare nZVI suspension and nZVI-laden foam, the spatial distribution of nZVI particles carried by SDS solution was significantly uniform along the column length. Third, the SDS concentration significantly influenced the migration of nZVI in porous media. The enhancement in the migration of nZVI carried by SDS solution was greater at an SDS dose of 0.25% compared with that at the other three doses (0.2%, 0.5%, and 1%) for sand with a 0.25 mm to 0.5 mm diameter. Increased SDS concentrations positively affected the transport of nZVI by foam for sand with a

Structure and electrochemistry of proteins harboring iron-sulfur clusters of different nuclearities. Part II. [4Fe-4S] and [3Fe-4S] iron-sulfur proteins.

PubMed

Zanello, Piero

2018-06-01

In the context of the plethora of proteins harboring iron-sulfur clusters we have already reviewed structure/electrochemistry of metalloproteins expressing single types of iron-sulfur clusters (namely: {Fe(Cys) 4 }, {[Fe 2 S 2 ](Cys) 4 }, {[Fe 2 S 2 ](Cys) 3 (X)} (X = Asp, Arg, His), {[Fe 2 S 2 ](Cys) 2 (His) 2 }, {[Fe 3 S 4 ](Cys) 3 }, {[Fe 4 S 4 ](Cys) 4 } and {[Fe 4 S 4 ](S γ Cys ) 3 (nonthiolate ligand)} cores) and their synthetic analogs. More recently we are focussing on structure/electrochemistry of metalloproteins harboring iron-sulfur centres of different nuclearities. Having started such a subject with proteins harboring [4Fe-4S] and [2Fe-2S] clusters, we now depict the state of art of proteins containing [4Fe-4S] and [3Fe-4S] clusters. Copyright © 2018 Elsevier Inc. All rights reserved.

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

PubMed

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

2018-02-15

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

Reduction of trichloroethylene and nitrate by zero-valent iron with peat.

PubMed

Min, Jee-Eun; Kim, Meejeong; Pardue, John H; Park, Jae-Woo

2008-02-01

The feasibility of using zero-valent iron (ZVI) and peat mixture as in situ barriers for contaminated sediments and groundwater was investigated. Trichloroethylene (TCE) and nitrate (NO(3)(-)), redox sensitive contaminants were reduced by ZVI and peat soil mixture under anaerobic condition. Peat was used to support the sorption of TCE, microbial activity for biodegradation of TCE and denitrification while TCE and nitrate were reduced by ZVI. Decreases in TCE concentrations were mainly due to ZVI, while peat supported denitrifying microbes and further affected the sorption of TCE. Due to the competition of electrons, nitrate reduction was inhibited by TCE, while TCE reduction was not affected by nitrate. From the results of peat and sterilized peat, it can be concluded that peat was involved in both dechlorination and denitrification but biological reduction of TCE was negligible compared to that of nitrate. The results from hydrogen and methane gas analyses confirmed that hydrogen utilization by microbes and methanogenic process had occurred in the ZVI-peat system. Even though effect of the peat on TCE reduction were quantitatively small, ZVI and peat contributed to the removal of TCE and nitrate independently. The 16S rRNA analysis revealed that viable bacterial diversity was narrow and the most frequently observed genera were Bacillus and Staphylococcus spp.

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

PubMed

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

2011-05-01

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

Local ordering and magnetism in Ga{sub 0.9}Fe{sub 3.1}N

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

Burghaus, Jens; Sougrati, Moulay T., E-mail: moulay-tahar.sougrati@univ-montp2.fr; Moechel, Anne

Prior investigations of the ternary nitride series Ga{sub 1-x}Fe{sub 3+x}N (0{<=}x{<=}1) have indicated a transition from ferromagnetic {gamma}'-Fe{sub 4}N to antiferromagnetic 'GaFe{sub 3}N'. The ternary nitride 'GaFe{sub 3}N' has been magnetically and spectroscopically reinvestigated in order to explore the weakening of the ferromagnetic interactions through the gradual incorporation of gallium into {gamma}'-Fe{sub 4}N. A hysteretic loop at RT reveals the presence of a minority phase of only 0.1-0.2 at%, in accord with the sound two-step synthesis. The composition of the gallium-richest phase 'GaFe{sub 3}N' was clarified by Prompt Gamma-ray Activation Analysis and leads to the berthollide formula Ga{sub 0.91(1)}Fe{sub 3.09(10)}N{submore » 1.05(7)}. Magnetic measurements indicate a transition around 8 K, further supported by Moessbauer spectral data. The weakening of the ferromagnetic coupling through an increasing gallium concentration is explained by a simple Stoner argument. In Ga{sub 0.9}Fe{sub 3.1}N, the presence of iron on the gallium site affects the magnetism by the formation of 13-atom iron clusters. - Graphical Abstract: The crystal structure of GaFe{sub 3}N with green nitrogen atoms in the very center, red iron atoms at the face centers, and gray gallium atoms at the corner positions. Highlights: > Almost phase-pure synthesis of Ga{sub 0.9}Fe{sub 3.1}N. > Prompt gamma-ray activation analysis yields precise composition. > Magnetic ordering of the facial Fe atoms at the lowest temperatures. > Moessbauer spectroscopy suggests percolation or RKKY-type interaction. > Fe{sub 13} clusters due to berthollide character.« less

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.

Sustaining 1,2-Dichloroethane Degradation in Nanoscale Zero-Valent Iron induced Fenton system by using Sequential H2O2 Addition at Natural pH

NASA Astrophysics Data System (ADS)

Phenrat, T.; Le, T. S. T.

2017-12-01

1,2-Dichloroethane (1,2-DCA) is a prevalent subsurface contaminant found in groundwater and soil around the world. Nanoscale zero-valent iron (NZVI) is a promising in situ remediation agent for chlorinated organics. Nevertheless, 1,2-DCA is recalcitrant to reductive dechlorination using NZVI. Chemical oxidation using Fenton's reaction with conventional Fe2+ is a valid option for 1,2-DCA remediation with a major technical challenge, i.e. aquifer acidification is needed to maintain Fe2+ for catalytic reaction. In this work, NZVI Fenton's process at neutral pH was applied to degrade 1,2-DCA at high concentration (2,000 mg/L) representing dissolved 1,2-DCA concentration close to non-aqueous phase liquid source zone. Instead of using acidification to maintain dissolved Fe2+ concentration, NZVI Fenton's process is self-catalytic based on oxidative dissolution of NZVI in the present of H2O2. Interfacial H+ is produced at NZVI surface to provide appropriate local pH which continuously releases Fe2+ for Fenton's reaction. Approximately, 87% of 1,2-DCA was degraded at neutral pH with the pseudo first-order rate constant of 0.98 hour-1 using 10 g/L of NZVI and 200 mM of H2O2. However, the reaction was prohibited quickly within 3 hours presumably due to the rapid depletion of H2O2. The application of sequential H2O2 addition provided a better approach to prevent rapid inhibition via controlling the H2O2 concentration in the system to be sufficient but not excess, thus resulting in the higher degradation efficiency (the pseudo first-order rate constant of 0.49 hour-1 and 99 % degradation in 8 hours). Using NZVI with sequential H2O2 addition was also successful in degrading 1,2-DCA sorbed on to soil, yielding 99% removal of 1,2-DCA within 16 hours at the rate constant of 0.23 hour-1, around two times slower than in the system without soil presumably due to rate-limited 1,2-DCA desorption from soil. Mechanistic understanding of how sequential addition of H2O2, in comparison to

Treatment of acid rock drainage using a sulfate-reducing bioreactor with zero-valent iron.

PubMed

Ayala-Parra, Pedro; Sierra-Alvarez, Reyes; Field, James A

2016-05-05

This study assessed the bioremediation of acid rock drainage (ARD) in flow-through columns testing zero-valent iron (ZVI) for the first time as the sole exogenous electron donor to drive sulfate-reducing bacteria in permeable reactive barriers. Columns containing ZVI, limestone or a mixture of both materials were inoculated with an anaerobic mixed culture and fed a synthetic ARD containing sulfuric acid and heavy metals (initially copper, and later also cadmium and lead). ZVI significantly enhanced sulfate reduction and the heavy metals were extensively removed (>99.7%). Solid-phase analyses showed that heavy metals were precipitated with biogenic sulfide in the columns packed with ZVI. Excess sulfide was sequestered by iron, preventing the discharge of dissolved sulfide. In the absence of ZVI, heavy metals were also significantly removed (>99.8%) due to precipitation with hydroxide and carbonate ions released from the limestone. Vertical-profiles of heavy metals in the columns packing, at the end of the experiment, demonstrated that the ZVI columns still had excess capacity to remove heavy metals, while the capacity of the limestone control column was approaching saturation. The ZVI provided conditions that enhanced sulfate reduction and generated alkalinity. Collectively, the results demonstrate an innovative passive ARD remediation process using ZVI as sole electron-donor. Copyright © 2016 Elsevier B.V. All rights reserved.

Crystal structure, phase transition and structural deformations in iron borate (Y0.95Bi0.05)Fe3(BO3)4 in the temperature range 90-500 K.

PubMed

Smirnova, Ekaterina S; Alekseeva, Olga A; Dudka, Alexander P; Artemov, Vladimir V; Zubavichus, Yan V; Gudim, Irina A; Bezmaterhykh, Leonard N; Frolov, Kirill V; Lyubutin, Igor S

2018-04-01

An accurate X-ray diffraction study of (Y 0.95 Bi 0.05 )Fe 3 (BO 3 ) 4 single crystals in the temperature range 90-500 K was performed on a laboratory diffractometer and used synchrotron radiation. It was established that the crystal undergoes a diffuse structural phase transition in the temperature range 350-380 K. The complexity of localization of such a transition over temperature was overcome by means of special analysis of systematic extinction reflections by symmetry. The transition temperature can be considered to be T str ≃ 370 K. The crystal has a trigonal structure in the space group P3 1 21 at temperatures of 90-370 K, and it has a trigonal structure in the space group R32 at 375-500 K. There is one type of chain formed by the FeO 6 octahedra along the c axis in the R32 phase. When going into the P3 1 21 phase, two types of nonequivalent chains arise, in which Fe atoms are separated from the Y atoms by a different distance. Upon lowering the temperature from 500 to 90 K, a distortion of the Y(Bi)O 6 , FeO 6 , B(2,3)O 3 coordination polyhedra is observed. The distances between atoms in helical Fe chains and Fe-O-Fe angles change non-uniformly. A sharp jump in the equivalent isotropic displacement parameters of O1 and O2 atoms within the Fe-Fe chains and fluctuations of the equivalent isotropic displacement parameters of B2 and B3 atoms were observed in the region of structural transition as well as noticeable elongation of O1, O2, B2, B3, Fe1, Fe2 atomic displacement ellipsoids. It was established that the helices of electron density formed by Fe, O1 and O2 atoms may be structural elements determining chirality, optical activity and multiferroicity of rare-earth iron borates. Compression and stretching of these helices account for the symmetry change and for the manifestation of a number of properties, whose geometry is controlled by an indirect exchange interaction between iron cations that compete with the thermal motion of atoms in the

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

PubMed

Hsu, Liang-Ching; Cho, Yen-Lin; Liu, Yu-Ting; Tzou, Yu-Min; Teah, Heng Yi

2018-06-01

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e - )] reacted with O 2(g) to generate H 2 O 2 at pH 1, only 60% of POM(e - ) was used to produce H 2 O 2 at pH 2. The remaining POM(e - ) was oxidized by the generated H 2 O 2 . Such additional consumption of POM(e - ) and H 2 O 2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e - ). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO 4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO 4 led to the incomplete As removal. Despite the loss of WO 4 , the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O 2 system into a practical strategy for As remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-10-01

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

Energies and spin states of FeS(0/-), FeS2(0/-), Fe2S2(0/-), Fe3S4(0/-), and Fe4S4(0/-) clusters.

PubMed

Li, Yan-Ni; Wang, Shengguang; Wang, Tao; Gao, Rui; Geng, Chun-Yu; Li, Yong-Wang; Wang, Jianguo; Jiao, Haijun

2013-04-15

The structures and energies of the electronic ground states of the FeS(0/-), FeS2(0/-), Fe2S2(0/-), Fe3S4(0/-), and Fe4S4(0/-) neutral and anionic clusters have been computed systematically with nine computational methods in combination with seven basis sets. The computed adiabatic electronic affinities (AEA) have been compared with available experimental data. Most reasonable agreements between theory and experiment have been found for both hybrid B3LYP and B3PW91 functionals in conjugation with 6-311+G* and QZVP basis sets. Detailed comparisons between the available experimental and computed AEA data at the B3LYP/6-311+G* level identified the electronic ground state of (5)Δ for FeS, (4)Δ for FeS(-), (5)B2 for FeS2, (6)A1 for FeS2(-), (1)A1 for Fe2S2, (8)A' for Fe2S2(-), (5)A'' for Fe3S4, (6)A'' for Fe3S4(-), (1)A1 for Fe4S4, and (1)A2 for Fe4S4(-). In addition, Fe2S2, Fe3S4, Fe3S4(-), Fe4S4, and Fe4S4(-) are antiferromagnetic at the B3LYP/6-311+G* level. The magnetic properties are discussed on the basis of natural bond orbital analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of anionic surfactant sodium dodecyl benzene sulfonate (SDBS) from wastewaters by zero-valent iron (ZVI): predominant removal mechanism for effective SDBS removal.

PubMed

Takayanagi, Akari; Kobayashi, Maki; Kawase, Yoshinori

2017-03-01

Mechanisms for removal of anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in wastewaters by zero-valent iron (ZVI) were systematically examined. The contributions of four removal mechanisms, i.e., reductive degradation, oxidative degradation, adsorption, and precipitation, changed significantly with solution pH were quantified and the effective removal of SDBS by ZVI was found to be attributed to the adsorption capability of iron oxides/hydroxides on ZVI surface at nearly neutral pH instead of the degradation at acidic condition. The fastest SDBS removal rate and the maximum TOC (total organic carbon) removal efficiency were obtained at pH 6.0. The maximum TOC removal at pH 6.0 was 77.8%, and the contributions of degradation, precipitation, and adsorption to TOC removal were 4.6, 14.9, and 58.3%, respectively. At pH 3.0, which is an optimal pH for oxidative degradation by the Fenton reaction, the TOC removal was only 9.8% and the contributions of degradation, precipitation, and adsorption to TOC removal were 2.3, 4.6, and 2.9%, respectively. The electrostatic attraction between dodecyl benzene sulfate anion and the iron oxide/hydroxide layer controlled the TOC removal of SDBS. The kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach could successfully describe the experimental results for SDBS removal by ZVI with the averaged correlation coefficient of 0.994. ZVI was found to be an efficient material toward the removal of anionic surfactant at nearly neutral pH under the oxic condition.

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.

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.

β-Li0.37Na0.63Fe(MoO4)2

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2014-01-01

The title compound, lithium/sodium iron(III) bis­[ortho­molyb­date(VI)], was obtained by a solid-state reaction. The main structure units are an FeO6 octa­hedron, a distorted MoO6 octa­hedron and an MoO4 tetra­hedron sharing corners. The crystal structure is composed of infinite double MoFeO11 chains along the b-axis direction linked by corner-sharing to MoO4 tetra­hedra so as to form Fe2Mo3O19 ribbons. The cohesion between ribbons via mixed Mo—O—Fe bridges leads to layers arranged parallel to the bc plane. Adjacent layers are linked by corners shared between MoO4 tetra­hedra of one layer and FeO6 octa­hedra of the other layer. The Na+ and Li+ ions partially occupy the same general position, with a site-occupancy ratio of 0.631 (9):0.369 (1). A comparison is made with AFe(MoO4)2 (A = Li, Na, K and Cs) structures. PMID:24764805

Electronic properties of excess Cr at Fe site in FeCr{sub 0.02}Se alloy

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

Kumar, Sandeep, E-mail: sandeepk.iitb@gmail.com; Singh, Prabhakar P.

2015-06-24

We have studied the effect of substitution of transition-metal chromium (Cr) in excess on Fe sub-lattice in the electronic structure of iron-selenide alloys, FeCr{sub 0.02}Se. In our calculations, we used Korringa-Kohn-Rostoker coherent potential approximation method in the atomic sphere approximation (KKR-ASA-CPA). We obtained different band structure of this alloy with respect to the parent FeSe and this may be reason of changing their superconducting properties. We did unpolarized calculations for FeCr{sub 0.02}Se alloy in terms of density of states (DOS) and Fermi surfaces. The local density approximation (LDA) is used in terms of exchange correlation potential.

Spin waves and magnetic exchange interactions in insulating Rb(0.89)Fe(1.58)Se(2).

PubMed

Wang, Miaoyin; Fang, Chen; Yao, Dao-Xin; Tan, GuoTai; Harriger, Leland W; Song, Yu; Netherton, Tucker; Zhang, Chenglin; Wang, Meng; Stone, Matthew B; Tian, Wei; Hu, Jiangping; Dai, Pengcheng

2011-12-06

The parent compounds of iron pnictide superconductors are bad metals with a collinear antiferromagnetic structure and Néel temperatures below 220 K. Although alkaline iron selenide A(y)Fe(1.6+x)Se(2) (A=K, Rb, Cs) superconductors are isostructural with iron pnictides, in the vicinity of the undoped limit they are insulators, forming a block antiferromagnetic order and having Néel temperatures of roughly 500 K. Here we show that the spin waves of the insulating antiferromagnet Rb(0.89)Fe(1.58)Se(2) can be accurately described by a local moment Heisenberg Hamiltonian. A fitting analysis of the spin wave spectra reveals that the next-nearest neighbour couplings in Rb(0.89)Fe(1.58)Se(2), (Ba,Ca,Sr)Fe(2)As(2), and Fe(1.05)Te are of similar magnitude. Our results suggest a common origin for the magnetism of all the Fe-based superconductors, despite having different ground states and antiferromagnetic orderings.

Demonstration of Combined Zero-Valent Iron and Electrical Resistance Heating for In Situ Trichloroethene Remediation

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

Truex, Michael J.; Macbeth, Tamzen; Vermeul, Vincent R.

The effectiveness of in situ treatment using zero-valent iron to remediate sites with non-aqueous phase or significant sediment-associated contaminant mass can be limited by relatively low rates of mass transfer to bring contaminants in contact with the reactive media. For a field test in a trichloroethene source area, combining moderate-temperature (maximum 50oC) subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate dechlorination and dissolution rates by a factor of 4 to 6 based on organic daughter products and a factor 8-16 using a chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilizationmore » at ambient groundwater temperature (~10oC) and as temperature was increased up to about 50oC. Increased reaction and contaminant dissolution were observed with increased temperature, but volatilization was minimal during the test because in situ reactions maintained low aqueous-phase TCE concentrations.« less

Photoreduction of Terrigenous Fe-Humic Substances Leads to Bioavailable Iron in Oceans.

PubMed

Blazevic, Amir; Orlowska, Ewelina; Kandioller, Wolfgang; Jirsa, Franz; Keppler, Bernhard K; Tafili-Kryeziu, Myrvete; Linert, Wolfgang; Krachler, Rudolf F; Krachler, Regina; Rompel, Annette

2016-05-23

Humic substances (HS) are important iron chelators responsible for the transport of iron from freshwater systems to the open sea, where iron is essential for marine organisms. Evidence suggests that iron complexed to HS comprises the bulk of the iron ligand pool in near-coastal waters and shelf seas. River-derived HS have been investigated to study their transport to, and dwell in oceanic waters. A library of iron model compounds and river-derived Fe-HS samples were probed in a combined X-ray absorption spectroscopy (XAS) and valence-to-core X-ray emission spectroscopy (VtC-XES) study at the Fe K-edge. The analyses performed revealed that iron complexation in HS samples is only dependent on oxygen-containing HS functional groups, such as carboxyl and phenol. The photoreduction mechanism of Fe III -HS in oceanic conditions into bioavailable aquatic Fe II forms, highlights the importance of river-derived HS as an iron source for marine organisms. Consequently, such mechanisms are a vital component of the upper-ocean iron biogeochemistry cycle.

Copper increases reductive dehalogenation of haloacetamides by zero-valent iron in drinking water: Reduction efficiency and integrated toxicity risk.

PubMed

Chu, Wenhai; Li, Xin; Bond, Tom; Gao, Naiyun; Bin, Xu; Wang, Qiongfang; Ding, Shunke

2016-12-15

The haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs), are highly cytotoxic and genotoxic, and typically occur in treated drinking waters at low μg/L concentrations. Since many drinking distribution and storage systems contain unlined cast iron and copper pipes, reactions of HAcAms with zero-valent iron (ZVI) and metallic copper (Cu) may play a role in determining their fate. Moreover, ZVI and/or Cu are potentially effective HAcAm treatment technologies in drinking water supply and storage systems. This study reports that ZVI alone reduces trichloroacetamide (TCAcAm) to sequentially form dichloroacetamide (DCAcAm) and then monochloroacetamide (MCAcAm), whereas Cu alone does not impact HAcAm concentrations. The addition of Cu to ZVI significantly improved the removal of HAcAms, relative to ZVI alone. TCAcAm and their reduction products (DCAcAm and MCAcAm) were all decreased to below detection limits at a molar ratio of ZVI/Cu of 1:1 after 24 h reaction (ZVI/TCAcAm = 0.18 M/5.30 μM). TCAcAm reduction increased with the decreasing pH from 8.0 to 5.0, but values from an integrated toxic risk assessment were minimised at pH 7.0, due to limited removal MCAcAm under weak acid conditions (pH = 5.0 and 6.0). Higher temperatures (40 °C) promoted the reductive dehalogenation of HAcAms. Bromine was preferentially removed over chlorine, thus brominated HAcAms were more easily reduced than chlorinated HAcAms by ZVI/Cu. Although tribromoacetamide was more easily reduced than TCAcAm during ZVI/Cu reduction, treatment of tribromoacetamide resulted in a higher integrated toxicity risk than TCAcAm, due to the formation of monobromoacetamide (MBAcAm). Copyright © 2016 Elsevier Ltd. All rights reserved.

Dissociative adsorption of CCl 4 on the Fe 3O 4(1 1 1)-(2×2) selvedge of α-Fe 2O 3(0 0 0 1)

NASA Astrophysics Data System (ADS)

Adib, K.; Mullins, D. R.; Totir, G.; Camillone, N.; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Osgood, R. M.

2003-02-01

The surface reactions of CCl 4 with the Fe 3O 4(1 1 1)-(2×2) selvedge of naturally occurring α-Fe 2O 3(0 0 0 1) single-crystals have been investigated using synchrotron X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). CCl 4 was found to dissociate on the Fe 3O 4 surface at 100 K producing chemisorbed Cl and adsorbed CCl 2. TPD shows that the large majority of the dissociatively adsorbed CCl 2 fragments extract lattice oxygen and desorb as phosgene at >275 K. However, the XPS spectra show no evidence for the formation of surface-bound phosgene, at 100 K, indicating that its formation involves two steps. The first step, dissociation, is spontaneous at 100 K, whereas the second, oxygen atom abstraction to form phosgene, requires thermal excitation. Cl chemisorption yielded two separate species, the mono- and dichloride terminations of surface iron sites. The identification of these two surface terminations is based on the coverage dependence and the surface temperature history of their Cl 2p 3/2 peak intensity. For example, heating to >450 K allows the monochloride to transform into iron dichloride, indicating Cl adatom mobility at these temperatures.

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.

Fe behavior in iron-bearing phonolitic and pantelleritic melts and its significance for magma dynamics in the volcanic conduits

NASA Astrophysics Data System (ADS)

Borovkov, Nikita; Hess, Kai-Uwe; Fehr, Karl-Thomas; Cimarelli, Corrado; Dingwell, Donald Bruce

2014-05-01

The style of volcanic eruptions is determined entirely by dynamics of magma ascent in conduits. Physical properties of a silicate melt, particulary viscosity, are responsible for fragmentation processes, bubble growth and their ascent, which are in their turn related to explosivity of eruptions. Therefore, comprehension of the macroscopic properties of silicate melts is required for adequate conduit modelling. Considering eruptions of Mt. Vesuvius, Italy, we observe that eruption style varies from strombolian to plinean and sub-plinean which is related to the changes of melts viscosity in conduits. At Vesuvius the composition of volcanic deposits (III phase) is mainly phonolitic with 5 - 8 wt. % FeO. Fe changes the valence and coordination depending on oxidation state. The changing of iron coordination causes increasing or decreasing viscosity because of the presence of higher or lower amounts of Fe species coordinated with stronger covalence bonds. Mossbauer spectra of iron-bearing natural pantelleritic and phonolitic glasses were studied to get data on speciation and coordination state of iron. Mössbauer spectroscopy measures hyperfine interactions (isomer shift (IS)) and quadrupole splitting (QS)) at Fe atoms embedded in glass structure, which provide the amount of ferric and ferrous iron and their coordination state depending on Redox conditions. Based on these data, we have considered redox-viscosity relationships and also iron coordination effects on viscosity of both mentioned natural melt compositions. For glasses, due to short range order, the Mössbauer spectra were fitted using mathematical procedures based on functional analysis (extended Voight lineshape included in "Recoil" and "Mosslab" software). Mössbauer spectra are deconvoluted in two sites: ferrous iron (IS=0,79-1,00 mm/s; QS= 1,78-2,25 mm/s) and ferric iron (IS=0,26-0,50 mm/s; QS= 0,75-0,95 mm/s). For both sites we observe that IS and QS gradually decrease towards more oxidized conditions

Immobilization of chromate in hyperalkaline waste streams by green rusts and zero-valent iron.

PubMed

Rogers, Christine M; Burke, Ian T; Ahmed, Imad A M; Shaw, Samuel

2014-01-01

Zero-valent iron (ZVI) and green rusts can be used as reductants to convert chromium from soluble, highly toxic Cr(VI) to insoluble Cr(III). This study compared the reduction rates of Cr(VI) by ZVI and two carbonate green rust phases in alkaline/hyperalkaline solutions. Batch experiments were carried out with synthetic chromate solutions at pH 7.7-12.3 and a chromite ore processing residue (COPR) leachate (pH approximately 12.2). Green rust removes chromate from high pH solutions (pH 10-12.5) very rapidly (<400 s). Chromate reduction rates for both green rust phases were consistently higher than for ZVI throughout the pH range studied; the surface area normalized rate constants were two orders of magnitude higher in the COPR leachate solution at pH 12.2. The performances of both green rusts were unaffected by changes in pH. In contrast, ZVI exhibited a marked decline in reduction rate with increasing pH to become almost ineffective above pH12.

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

PubMed

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

2017-01-01

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

Rapid and extensive debromination of decabromodiphenyl ether by smectite clay-templated subnanoscale zero-valent iron.

PubMed

Yu, Kai; Gu, Cheng; Boyd, Stephen A; Liu, Cun; Sun, Cheng; Teppen, Brian J; Li, Hui

2012-08-21

Subnanoscale zerovalent iron (ZVI) synthesized using smectite clay as a template was utilized to investigate reduction of decabromodiphenyl ether (DBDE). The results revealed that DBDE was rapidly debrominated by the prepared smectite-templated ZVI with a reaction rate 10 times greater than that by conventionally prepared nanoscale ZVI. This enhanced reduction is plausibly attributed to the smaller-sized smectite-templated ZVI clusters (∼0.5 nm) vs that of the conventional nanoscale ZVI (∼40 nm). The degradation of DBDE occurred in a stepwise debromination manner. Pentabromodiphenyl ethers were the terminal products in an alkaline suspension (pH 9.6) of smectite-templated ZVI, whereas di-, tri-, and tetrabromodiphenyl ethers formed at the neutral pH. The presence of tetrahydrofuran (THF) as a cosolvent at large volume fractions (e.g., >70%) in water reduced the debromination rates due to enhanced aggregation of clay particles and/or diminished adsorption of DBDE to smectite surfaces. Modification of clay surfaces with tetramethylammonium (TMA) attenuated the colsovent effect on the aggregation of clay particles, resulting in enhanced debromination rates. Smectite clay provides an ideal template to form subnanoscale ZVI, which demonstrated superior debromination reactivity with DBDE compared with other known forms of ZVIs. The ability to modify the nature of smectite clay surface by cation exchange reaction utilizing organic cations can be harnessed to create surface properties compatible with various contaminated sites.

[Reduction of nitrobenzene by iron oxides bound Fe(II) system at different pH values].

PubMed

Luan, Fu-Bo; Xie, Li; Li, Jun; Zhou, Qi

2009-07-15

Batch tests were conducted to investigate the reductive transformation of nitrobenzene by goethite, hematite, magnetite and steel converter slag bound Fe(II) system. And the reduction mechanism was explored at different pH values. Experimental results showed that hematite, magnetite and steel converter slag could adsorb Fe(II) on surfaces and form iron oxides bound Fe(II) system at pH from 6.5 to 7.0. The systems had strong reductive capacity and could reduce nitrobenzene to aniline. The reduction efficiency of nitrobenzene in surface bound Fe(II) system followed the sequence of magnetite, hematite and steel converter slag from high to low. The reduction efficiency of hematite and magnetite system increased with pH increasing. While it was almost pH independent in steel converter slag system. Although goethite adsorbed most of Fe(II) in solution, the adsorbed Fe(II) had no reductive activity for nitrobenzene. At pH 6.0, small amount of Fe(II) was adsorbed on magnetite and hematite and the systems did not show reductive activity for nitrobenzene. However, steel converter slag could adsorb Fe(II) at pH 6.0 and reduction efficiency almost equaled to the value at pH 7.0. When pH was above 7.5, dissolved Fe(II) could be converted to Fe(OH)2 and the newly formed Fe(OH)2 became the main redactor in the system. Under alkali condition, the presence of iron oxides inhibited the reduction capacity of system.

Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

PubMed

Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G

2002-10-15

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

Synthesis of quenchable high-pressure form of magnetite (h-Fe3O4) with composition [4](Fe0.732+ Mg0.26)[6](Fe0.713+ Cr0.14Al0.10 Si0.04)2O4

NASA Astrophysics Data System (ADS)

Koch-Müller, Monika; Mugnaioli, Enrico; Rhede, Dieter; Speziale, Sergio; Kolb, Ute; Wirth, Richard

2014-05-01

Cubic inverse-spinel magnetite transforms under pressure to orthorhombic normal-spinel magnetite, h-Fe3O4 ( e.g. Fei et al. 1999; Bengtson et al. 2013). The pressure at which the transition takes place is still controversial. The high-pressure form is reported to be not quenchable to ambient conditions. We report the synthesis of h-magnetite which incorporates considerable amounts of additional cations (Cr, Mg, Al, Si) and is quenchable to ambient conditions. Two experiments were performed at 18 GPa and 1800 ° C in a multi-anvil press. The run products were investigated by electron microprobe, transmission electron microscopy and electron diffraction tomography. We observed the formation of h-magnetite in both experiments. In experiment MA-367 we used an oxide mixture with a majoritic stoichiometry Mg1.8Fe1.2(Al1.4 Cr0.2Si0.2Mg0.2)Si3O12 as starting material, with Si and Mg in excess. The Fe-oxide phase forms elongated aggregates 10-30 μm in length, mutually intergrown with majorite, the latter being the main phase of the run products coexisting with small amounts of stishovite. The formula for h-magnetite in run MA-367 was calculated as [4](Fe0.732+ Mg0.26)[6](Fe0.713+ Cr0.14Al0.10 Si0.04)2O4. In the second experiment (MA-376) we used an oxide mixture corresponding to the composition of h-magnetite obtained in MA-367. In this experiment the main phase was h-magnetite with composition [4](Fe0.982+)[6](Fe0.683+ Cr0.17Al0.13 Si0.02)2O4coexisting with very small amounts of wadsleyite. Interestingly no magnesium was incorporated into the Fe-oxide in this experiment compared to MA-367 and no iron was found in the coexisting wadsleyite. For the first time it was possible to perform electron diffraction on recovered h-magnetite of both experiments and we observed that -at least in our case- the h-magnetite structure can better be described in space group Amam than in space group Bbmm as previously proposed. The substitution of Fe by Cr, Mg, Al and Si, all smaller in

Charge dynamics of 57Fe probe atoms in La2Li0.5Cu0.5O4

NASA Astrophysics Data System (ADS)

Presniakov, I. A.; Sobolev, A. V.; Rusakov, V. S.; Moskvin, A. S.; Baranov, A. V.

2018-06-01

The objective of this study is to characterize the electronic state and local surrounding of 57Fe Mössbauer probe atoms within iron-doped layered perovskite La2Li0.5Cu0.5O4 containing transition metal in unusual formal oxidation states "+3". An approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that a large amount of charge is transferred via Cu-O bonds from the O: 2p bands to the Cu: 3d orbitals and the ground state is dominated by the d9L configuration ("Cu2+-O-" state). The dominant d9L ground state for the (CuO6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe3+ + O-(L) → Fe4+ + O2-, which transforms "Fe3+" into "Fe4+" state. The experimental spectra in the entire temperature range 77-300 K were described with the use of the stochastic two-level model based on the assumption of dynamic equilibrium between two Fe3+↔Fe4+ valence states related to the iron atom in the [Fe(1)O4]4- center. The relaxation frequencies and activation energies of the corresponding charge fluctuations were estimated based on Mössbauer data. The results are discussed assuming a temperature-induced change in the electronic state of the [CuO4]5- clusters in the layered perovskite.

Non-pumping reactive wells filled with mixing nano and micro zero-valent iron for nitrate removal from groundwater: Vertical, horizontal, and slanted wells

NASA Astrophysics Data System (ADS)

Hosseini, Seiyed Mossa; Tosco, Tiziana; Ataie-Ashtiani, Behzad; Simmons, Craig T.

2018-03-01

Non-pumping reactive wells (NPRWs) filled by zero-valent iron (ZVI) can be utilized for the remediation of groundwater contamination of deep aquifers. The efficiency of NPRWs mainly depends on the hydraulic contact time (HCT) of the pollutant with the reactive materials, the extent of the well capture zone (Wcz), and the relative hydraulic conductivity of aquifer and reactive material (Kr). We investigated nitrate removal from groundwater using NPRWs filled by ZVI (in nano and micro scales) and examined the effect of NPRWs orientations (i.e. vertical, slanted, and horizontal) on HCT and Wcz. The dependence of HCT on Wcz for different Kr values was derived theoretically for a homogeneous and isotropic aquifer, and verified using particle tracking simulations performed using the semi-analytical particle tracking and pathlines model (PMPATH). Nine batch experiments were then performed to investigate the impact of mixed nano-ZVI, NZVI (0 to 2 g l-1) and micro-ZVI, MZVI (0 to 4 g l-1) on the nitrate removal rate (with initial NO3-=132 mg l-1). The NPRWs system was tested in a bench-scale sand medium (60 cm length × 40 cm width × 25 cm height) for three orientations of NPRWs (vertical, horizontal, and slanted with inclination angle of 45°). A mixture of nano/micro ZVI, was used, applying constant conditions of pore water velocity (0.024 mm s-1) and initial nitrate concentration (128 mg l-1) for five pore volumes. The results of the batch tests showed that mixing nano and micro Fe0 outperforms these individual materials in nitrate removal rates. The final products of nitrate degradation in both batch and bench-scale experiments were NO2-, NH4+, and N2(gas). The results of sand-box experiments indicated that the slanted NPRWs have a higher nitrate reduction rate (57%) in comparison with vertical (38%) and horizontal (41%) configurations. The results also demonstrated that three factors have pivotal roles in expected HCT and Wcz, namely the contrast between the hydraulic

Effects of a Tripeptide Iron on Iron-Deficiency Anemia in Rats.

PubMed

Xiao, Chen; Lei, Xingen; Wang, Qingyu; Du, Zhongyao; Jiang, Lu; Chen, Silu; Zhang, Mingjie; Zhang, Hao; Ren, Fazheng

2016-02-01

This study aims to investigate the effects of a tripeptide iron (REE-Fe) on iron-deficiency anemia rats. Sprague-Dawley rats were randomly divided into seven groups: a normal control group, an iron-deficiency control group, and iron-deficiency groups treated with ferrous sulfate (FeSO4), ferrous glycinate (Fe-Gly), or REE-Fe at low-, medium-, or high-dose groups. The rats in the iron-deficiency groups were fed on an iron-deficient diet to establish iron-deficiency anemia (IDA) model. After the model established, different iron supplements were given to the rats once a day by intragastric administration for 21 days. The results showed that REE-Fe had effective restorative action returning body weight, organ coefficients, and hematological parameters in IDA rats to normal level. In addition, comparing with FeSO4 or Fe-Gly, high-dose REE-Fe was more effective on improving the levels of renal coefficient, total iron-binding capacity, and transferrin. Furthermore, the liver hepcidin messenger RNA (mRNA) expression in the high-dose group was significantly higher (p < 0.05) than that in the FeSO4 or Fe-Gly group and showed no significant difference (p > 0.05) with the normal control group. The findings suggest that REE-Fe is an effective source of iron supplement for IDA rats and might be exploited as a new iron fortifier.

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.

The role of FeS(aq) molecular clusters in microbial redox cycling and iron mineralization.

NASA Astrophysics Data System (ADS)

Druschel, G.; Oduro, H.; Sperling, J.; Johnson, C.

2008-12-01

Iron sulfide molecular clusters, FeS(aq), are a group of polynuclear Fe-S complexes varying in size between a few and a few hundred molecules that occur in many environments and are critical parts of cycling between soluble iron and iron sulfide minerals. These clusters react uniquely with voltammetric Au-amalgam electrodes, and the signal for these molecules has now been observed in many terrestrial and marine aquatic settings. FeS(aq) clusters form when aqueous sulfide and iron(II) interact, but the source of those ions can come from abiotic or microbial sulfate and iron reduction or from the abiotic non-oxidative dissolution of iron sulfide minerals. Formation of iron sulfide minerals, principally mackinawite as the first solid nanocrystalline phase in many settings, is necessarily preceeded by formation and evolution of these molecular clusters as mineralization proceeds, and the clusters have been suggested to additionally be part of the pyritization process (Rickard and Luther, 1997; Luther and Rickard, 2005). In several systems, we have also observed FeS(aq) clusters to be the link between Fe-S mineral dissolution and oxidation of iron and sulfide, with important implications for changes to the overall oxidation pathway. Microorganisms can clearly be involved in the formation of FeS(aq) through iron and sulfate reduction, but it is not clear to date if organisms can utilize these clusters either as metabolic components or as anabolic 'building blocks' for enzyme production. Cycling of iron in the Fe-S system linked to FeS(aq) would clearly be a critical part of understanding iron isotope dynamics preserved in iron sulfide minerals. We will review ongoing work towards understanding the role of FeS(aq) in iron cycling and isotope fractionation as well as the measurement and characterization of this key class of iron complexes using environmental voltammetry.

Rapid synthesis of Fe-doped CuO-Ce0.8Zr0.2O2 catalysts for CO preferential oxidation in H2-rich streams: Effect of iron source and the ratio of Fe/Cu

NASA Astrophysics Data System (ADS)

Wang, Jing; Han, Caiyun; Gao, Xiaoya; Lu, Jichang; Wan, Gengpin; He, Dedong; Chen, Ran; Chen, Kezhen; He, Sufang; Luo, Yongming

2017-03-01

A facile route (urea grind combustion method) is described for the rapid synthesis of Fe-doped Cu-Ce-Zr catalysts within 30 min through simple grinding and combustion. The effects of iron source and Fe/Cu mass ratio on the performances of the catalysts for CO preferential oxidation (CO-PROX) are evaluated. The influences of H2O, CO2, and their mixture on the activity as well as stability of the catalysts are also investigated. The samples are characterized by XRD, N2 adsorption-desorption, H2-TPR, TEM, Raman and XPS. Fe(NO3)3 is found to be superior to FeCl3 and Fe2(SO4)3 as the iron source for Fe-CuCZ catalyst. Among the different synthesized catalysts, 1/10Fe(N)-CuCZ is found to be the most active catalyst, indicating that the optimal Fe/Cu mass ratio is 1/10. The influences of H2O, CO2, and H2O + CO2 on the catalytic performance of 1/10Fe(N)-CuCZ are in the order of CO2 < CO2 + H2O < H2O. 1/10Fe(N)-CuCZ exhibits excellent stability during a 228 h time-on-stream test. 1/10Fe(N)-CuCZ shows the highest catalytic activity and excellent stability even in the presence of H2O and CO2. The excellent catalytic performance can be attributed to the synergy between the highly dispersed copper species and ceria, as well as the formation of more oxygen vacancies and reduced copper species.

Environmental application of millimetre-scale sponge iron (s-Fe0) particles (IV): New insights into visible light photo-Fenton-like process with optimum dosage of H2O2 and RhB photosensitizers.

PubMed

Ju, Yongming; Yu, Yunjiang; Wang, Xiaoyan; Xiang, Mingdeng; Li, Liangzhong; Deng, Dongyang; Dionysiou, Dionysios D

2017-02-05

In this study, we firstly develop the photo-Fenton-like system with millimetric sponge iron (s-Fe 0 ), H 2 O 2 , visible light (vis, λ≥420nm) and rhodamine B (RhB), and present a comprehensive study concerning the mechanism. Thus, we investigate (1) the adsorption of RhB onto s-Fe 0 , (2) the photo-Fenton-like removal of RhB over iron oxides generated from the corrosion of s-Fe 0 , (3) the homogeneous photo-Fenton removal of RhB over Fe 2+ or Fe 3+ , (4) the Fe 3+ -RhB complexes, and (5) the photo-Fenton-like removal of tetrabromobisphenol A (TBBPA). The results show that neither the adsorption process over s-Fe 0 nor the photo-Fenton-like process over FeOOH, Fe 3 O 4 and Fe 2 O 3 , achieved efficient removal of RhB. For comparison, in homogeneous photo-Fenton process, the presence of Fe 3+ ions, rather than Fe 2+ ions, effectively eliminated RhB. Furthermore, the UV-vis spectra showing new absorbance at∼285nm indicate the complexes of RhB and Fe 3+ ions, adopting vis photons to form excited state and further eject one electron via ligand-to-metal charge-transfer to activate H 2 O 2 . Additionally, efficient TBBPA removal was obtained only in the presence of RhB. Accordingly, the s-Fe 0 - based photo-Fenton-like process assisted with dyestuff wastewater is promising for removing a series of persistent organic pollutants. Copyright © 2016 Elsevier B.V. All rights reserved.

Upgrade Recycling of Cast Iron Scrap Chips towards β-FeSi₂ Thermoelectric Materials.

PubMed

Laila, Assayidatul; Nanko, Makoto; Takeda, Masatoshi

2014-09-04

The upgrade recycling of cast-iron scrap chips towards β-FeSi₂ thermoelectric materials is proposed as an eco-friendly and cost-effective production process. By using scrap waste from the machining process of cast-iron components, the material cost to fabricate β-FeSi₂ is reduced and the industrial waste is recycled. In this study, β-FeSi₂ specimens obtained from cast iron scrap chips were prepared both in the undoped form and doped with Al and Co elements. The maximum figure of merit ( ZT ) indicated a thermoelectric performance of approximately 70% in p-type samples and nearly 90% in n-type samples compared to β-FeSi₂ prepared from pure Fe and other published studies. The use of cast iron scrap chips to produce β-FeSi₂ shows promise as an eco-friendly and cost-effective production process for thermoelectric materials.

Magnetic Moments and Hyperfine Parameters of Fe3-xCrxAl0.5Si0.5

NASA Astrophysics Data System (ADS)

Rećko, Katarzyna; Go, Anna; Satuła, Dariusz; Biernacka, Maria; Dobrzyński, Ludwik; Waliszewski, Janusz; Milczarek, Jacek J.; Szymański, Krzysztof

2012-04-01

Results of X-ray, neutron, magnetization and Mössbauer measurements on polycrystalline samples of Fe3-xCrx Al0.5Si0.5 (x=0, 0.125, 0.250, 0.375, and 0.5) alloys, crystallizing in DO3 type of structure, are presented. X-ray and neutron diffraction confirmed the phase homogeneity of all the samples. The unit cell volume has been proved to be independent of the chromium content. Neutron and Mössbauer measurements disclosed that Cr atoms occupy preferentially B-sites, while D-sites are almost entirely occupied by Al and Si. The total magnetisation as well as the individual magnetic moments μFe(A,C), μFe(B) and μCr(B,D) have been found to vary linearly with chromium concentration. Influence of local environments on the formation of magnetic moments in Fe3Al0.5Si0.5 when chromium is substituted for iron was examined using self-consistent spin-polarized tight-binding linear muffin-tin orbital method (TB-LMTO).

Ab initio Studies of Magnetism in the Iron Chalcogenides FeTe and FeSe

NASA Astrophysics Data System (ADS)

Hirayama, Motoaki; Misawa, Takahiro; Miyake, Takashi; Imada, Masatoshi

2015-09-01

The iron chalcogenides FeTe and FeSe belong to the family of iron-based superconductors. We study the magnetism in these compounds in the normal state using the ab initio downfolding scheme developed for strongly correlated electron systems. In deriving ab initio low-energy effective models, we employ the constrained GW method to eliminate the double counting of electron correlations originating from the exchange correlations already taken into account in the density functional theory. By solving the derived ab initio effective models, we reveal that the elimination of the double counting is important in reproducing the bicollinear antiferromagnetic order in FeTe, as is observed in experiments. We also show that the elimination of the double counting induces a unique degeneracy of several magnetic orders in FeSe, which may explain the absence of the magnetic ordering. We discuss the relationship between the degeneracy and the recently found puzzling phenomena in FeSe as well as the magnetic ordering found under pressure.

Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

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

Bykova, E., E-mail: elena.bykova@uni-bayreuth.de; Laboratory of Crystallography, University of Bayreuth, D-95440 Bayreuth; Gou, H.

2015-10-15

We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for highmore » bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.« less