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Sample records for emulsified zero-valent iron

  1. Application of Emulsified Zero-Valent Iron to Marine Environments

    NASA Technical Reports Server (NTRS)

    Brooks, Kathleen B.; Quinn, Jacqueline W.; Clausen, Christian A.; Geiger, Cherie L.

    2005-01-01

    Contamination of marine waters and sediments with heavy metals and dense non-aqueous phase liquids (DNAPLs) including chlorinated solvents, pesticides and PCBs pose ecological and human health risks through the contaminant's potential bioaccumulation in fish, shellfish and avian populations. The contaminants enter marine environments through improper disposal techniques and storm water run-off. Current remediation technologies for application to marine environments include costly dredging and off-site treatment of the contaminated media. Emulsified zero-valent iron (EZVI) has been proven to effectively degrade dissolved-phase and DNAPL-phase contaminants in freshwater environments on both the laboratory and field-scale level. However, the application to marine environments is only just being explored. This paper discusses the potential use of EZVI in brackish and saltwater environments, with supporting laboratory data detailed. Laboratory studies were performed in 2005 to establish the effectiveness of EZVI to degrade trichloroethylene (TCE) in saltwater. Headspace vials were setup to determine the kinetic rate of TCE degradation using EZVI in seawater. The reaction vials were analyzed by Gas Chromatographic/Flame Ionization Detection (GC/FID) for ethene production after a 48 day period using a GC/FID Purge and Trap system. Analytical results showed that EZVI was very effective at degrading TCE. The reaction by-products (ethene, acetylene and ethane) were produced at 71% of the rate in seawater as in the fresh water controls. Additionally, iron within the EZVI particles was protected from oxidation of the corrosive seawater, allowing EZVI to perform in an environment where zero-valent iron alone could not compete. Laboratory studies were also performed to establish the effectiveness of emulsified zero-valent metal (EZVM) to remove dissolved-phase cadmium and lead found in seawater. EZVM is comprised of a combination of magnesium and iron metal surrounded by the

  2. Application of Emulsified Zero-Valent Iron to Marine Environments

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline W.; Brooks, Kathleen B.; Geiger, Cherie L.; Clausen, Christian A.; Milum, Kristen M.

    2006-01-01

    Contamination of marine waters and sediments with heavy metals and dense non-aqueous phase liquids (DNAPLs) including chlorinated solvents, pesticides and PCBs pose ecological and human health risks through the potential of the contaminant to bioaccumulate in fish, shellfish and avian populations. The contaminants enter marine environments through improper disposal techniques and storm water runoff. Current remediation technologies for application to marine environments include costly dredging and off-site treatment of the contaminated media. Emulsified zero-valent iron (EZVI) has been proven to effectively degrade dissolved-phase and DNAPL-phase contaminants in freshwater environments on both the laboratory and field-scale level. Emulsified Zero-Valent Metal (EZVM) using metals such as iron and/or magnesium have been shown in the laboratory and on the bench scale to be effective at removing metals contamination in freshwater environments. The application to marine environments, however, is only just being explored. This paper discusses. the potential use of EZVI or EZVM in brackish and saltwater environments, with supporting laboratory data detailing its effectiveness on trichloroethylene, lead, copper, nickel and cadmium.

  3. FIELD EVALUATION OF THE TREATMENT OF DNAPL USING EMULSIFIED ZERO-VALENT IRON (BATTELLE PRESENTATION)

    EPA Science Inventory

    A pilot scale field demonstration of dense non-aqueous phase liquids (DNAPL) treatment using emulsified zero-valent iron (EZVI) is being conducted at Parris Island Marine Corps Recruit Depot (MCRD), Parris Island SC. The EZVI technology was developed at the University of Central ...

  4. FIELD EVALUATION OF THE TREATMENT OF DNAPL USING EMULSIFIED ZERO-VALENT IRON (Battelle Conference)

    EPA Science Inventory

    A pilot scale field demonstration of dense non-aqueous phase liquids (DNAPL) treatment using emulsified zero-valent iron (EZVI) was conducted at Parris Island Marine Corps Recruit Depot (MCRD), Parris Island, SC. The EZVI technology was developed at the University of Central Fl...

  5. FIELD EVALUATION OF THE TREATMENT OF DNAPL USING EMULSIFIED ZERO-VALENT IRON

    EPA Science Inventory

    A pilot scale field demonstration of dense non-aqueous phase liquids (DNAPL) treatment using emulsified zero-valent iron (EZVI) is being conducted at Parris Island Marine Corps Recruit Depot (MCRD), Parris Island SC. The demonstration is being conducted by Geosyntec, the Nationa...

  6. FIELD EVALUATION OF THE TREATMENT OF DNAPL USING EMULSIFIED ZERO-VALENT IRON (DNAPL CONFERENCE)

    EPA Science Inventory

    A pilot scale field demonstration of dense non-aqueous phase liquids (DNAPL) treatment using emulsified zero-valent iron (EZVI) is being conducted at Parris Island Marine Corps Recruit Depot (MCRD), Parris Island SC. The demonstration is being conducted by Geosyntec, the Nationa...

  7. Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline; Geiger, Cherie; Clausen, Chris; Brooks, Kathleen; Coon, Christina; O'Hara, Suzanne; Krug, Thomas; Major, David; Yoon, Sam; Gavaskar, Arun; Holdsworth, Thomas

    2004-01-01

    This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nano-scale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, non-aqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (V005) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

  8. Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline; Geiger, Cherie; Clausen, Chris; Brooks, Kathleen; Coon, Christina; O'Hara, Suzanne; Krug, Thomas; Major, David; Yoon, Woong-Sang; Gavaskar, Arun; Holdsworth, Thomas

    2005-01-01

    This paper describes the results of the first field-scale demonstration conducted to evaluate the performance of nanoscale emulsified zero-valent iron (EZVI) injected into the saturated zone to enhance in situ dehalogenation of dense, nonaqueous phase liquids (DNAPLs) containing trichloroethene (TCE). EZVI is an innovative and emerging remediation technology. EZVI is a surfactant-stabilized, biodegradable emulsion that forms emulsion droplets consisting of an oil-liquid membrane surrounding zero-valent iron (ZVI) particles in water. EZVI was injected over a five day period into eight wells in a demonstration test area within a larger DNAPL source area at NASA's Launch Complex 34 (LC34) using a pressure pulse injection method. Soil and groundwater samples were collected before and after treatment and analyzed for volatile organic compounds (VOCs) to evaluate the changes in VOC mass, concentration and mass flux. Significant reductions in TCE soil concentrations (>80%) were observed at four of the six soil sampling locations within 90 days of EZVI injection. Somewhat lower reductions were observed at the other two soil sampling locations where visual observations suggest that most of the EZVI migrated up above the target treatment depth. Significant reductions in TCE groundwater concentrations (57 to 100%) were observed at all depths targeted with EZVI. Groundwater samples from the treatment area also showed significant increases in the concentrations of cis-1,2-dichloroethene (cDCE), vinyl chloride (VC) and ethene. The decrease in concentrations of TCE in soil and groundwater samples following treatment with EZVI is believed to be due to abiotic degradation associated with the ZVI as well as biodegradation enhanced by the presence of the oil and surfactant in the EZVI emulsion.

  9. Zero-valent iron nanoparticles preparation

    SciTech Connect

    Oropeza, S.; Corea, M.; Gómez-Yáñez, C.; Cruz-Rivera, J.J.; Navarro-Clemente, M.E.

    2012-06-15

    Graphical abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}] at room temperature and a pressure of 3 atm. The synthesized nanoparticles were spherical and had diameters less than 5 nm. Highlights: ► Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}]. ► The conditions of reaction were at room temperature and a pressure of 3 atm. ► The synthesized nanoparticles were spherical and had diameters less than 5 nm. -- Abstract: Zero-valent iron nanoparticles were synthesized by hydrogenating [Fe[N(Si(CH{sub 3}){sub 3}){sub 2}]{sub 2}] at room temperature and a pressure of 3 atm. To monitor the reaction, a stainless steel pressure reactor lined with PTFE and mechanically stirred was designed. This design allowed the extraction of samples at different times, minimizing the perturbation in the system. In this way, the shape and the diameter of the nanoparticles produced during the reaction were also monitored. The results showed the production of zero-valent iron nanoparticles that were approximately 5 nm in diameter arranged in agglomerates. The agglomerates grew to 900 nm when the reaction time increased up to 12 h; however, the diameter of the individual nanoparticles remained almost the same. During the reaction, some byproducts constituted by amino species acted as surfactants; therefore, no other surfactants were necessary.

  10. Dechlorination of pentachlorophenol by zero valent iron and modified zero valent irons

    SciTech Connect

    Kim, Y.H.; Carraway, E.R.

    2000-05-15

    The disappearance of pentachlorophenol (PCP) from aqueous solutions in contact with zero valent metals (ZVMs) may be due to dechlorination reactions or sorption to ZVM-related surfaces. Previously reported results on PCP and zero valent iron measured only PCP loss from aqueous solutions and attributed this loss to reaction. In this study, the total amount of unreacted PCP, both that in aqueous solution and that sorbed to ZVM-related surfaces, was measured using a modified extraction method. PCP dechlorination was confirmed by following the appearance of tetrachlorophenol isomers. The results indicate that the rate of dechlorination is much slower than previously reported. In their experiments, electrolytic zero valent iron with a surface area of 0.12 m{sup 2}/g resulted in an observed first-order rate constant of 3.9 x 10{sup {minus}3} h{sup {minus}1} or a half-life of approximately 7.4 days. Normalized to surface area, the rate constant (k{sub SA}) is 3.2 x 10{sup {minus}4} L m{sup {minus}2} h{sup {minus}1}. Four amended irons prepared by coating iron with palladium (Pd/Fe), platinum (Pt/Fe), nickel (Ni/Fe), and copper (Cu/Fe) were also used and showed slower removal rates as compared to unamended iron. Slower reaction rates obtained with amended irons as compared to iron have not been previously reported. Overall, this study conclusively demonstrates PCP dechlorination by iron and several bimetallic ZVMs and indicates that it is essential to separate reaction and sorption processes.

  11. TREATMENT OF GROUND WATER WITH ZERO VALENT IRON (ZVI)

    EPA Science Inventory

    A presentation on the use of zero valent iron (ZVI) for groundwater remediation at the Memphis Defense Depot Site in Memphis, TN, will be given at a public meeting in Memphis on February 24. The presentation is being given in response to a request by a citizen's group associated...

  12. DDT, DDD, AND DDE DECHLORINATION BY ZERO-VALENT IRON

    EPA Science Inventory

    Traditionally, destruction of DDT [1,1,1-trichIoro-2,2-bis(p-chlorophenyl)ethane] for environmental remediation required high-energy processes such as incineration. Here, the capability of powdered zero-valent iron to dechlorinate DDT and related compounds at room tempera...

  13. Feasibility of amending slurry walls with zero-valent iron

    SciTech Connect

    Rabideau, A.J.; Shen, P.; Khandelwal, A.

    1999-04-01

    Rapid degradation of aqueous trichloroethylene (TCE) was observed in batch experiments conducted with soil/bentonite slurry wall materials amended with the addition of zero-valent iron. The first-order TCE decay constants for soil/bentonite/iron mixtures, when normalized to the available iron surface area, were approximately 1--2 orders of magnitude higher than observed in batch experiments with pure iron systems. Permeability tests indicated an increase in SB hydraulic conductivity roughly proportional to the amount of iron added. Based on the observed reaction rates and the assumption of sustained long-term performance, significantly less than one percent added iron would be required to reduce the diffusive flux of TCE across an installed slurry wall by over 10 orders of magnitude. However, the release of hydrogen gas was noted as a potential problem for low permeability systems containing zero-valent iron.

  14. Synthesis, Characterization, and Properties of Zero-Valent Iron Nanoparticles

    SciTech Connect

    Baer, Donald R.; Tratnyek, P. G.; Qiang, You; Amonette, James E.; Linehan, John C.; Sarathy, Vaishnavi; Nurmi, J. T.; Wang, Chong M.; Antony, Jiji

    2007-04-04

    This chapter provides an overview of synthesis, characterization and property measurements techniques important for making understanding the nature of zero valent iron nanoparticles. The chemical reactivity of nanometer-sized materials can be quite different from that of either bulk forms of a material or the individual atoms and molecules that comprise it. Advances in our ability to synthesize, visualize, characterize and model these materials have created new opportunities to control the rates and products of chemical reactions in ways not previously possible. Zero valent iron (ZVI), including non-nanoparticle forms for iron, is one of the most promising remediation technologies for the removal of mobile chlorinated hydrocarbons and reducible inorganic anions for ground water. ZVI nanoparticles may have great potential to assist environmental remediation, but there are significant scientific and technological questions that remain to be answered. Understanding of ZVI reactive metal core-shell nanoparticles requires use of particles that are as well characterized and understood as possible. In this chapter we describe the issues and provide examples that include synthesis of nanoparticles, analytical characterization of the particles and finally measurements of their chemical properties.

  15. Reductive dehalogenation of trichloroethylene using zero-valent iron

    SciTech Connect

    Gotpagar, J.; Grulke, E.; Bhattacharyya, D.

    1997-12-31

    Reductive dehalogenation of hazardous organics using zero-valent metals is a promising technology. The purpose of this study was to examine the effect of feed concentration, initial pH, metal loading and particle size of metal on the degradation of trichloroethylene (TCE), using zero-valent iron. The degradation rate was found to be first order with respect to the organic molecule, thus the conversion was independent of initial TCE concentration. The amount of TCE degraded at any given time was found to be directly proportional to the dissolved iron in solution. The metal surface area plays a crucial role in the process. Twofold increase in the pseudo first order rate constant was obtained when the metal particle size was decreased from 370 {mu}m by factor of 2.5. For iron surface area per unit volume (S/V) of solution < 1000 m{sup -1}, the TCE degradation rate constant increased linearly with S/V ratio. 20 refs., 8 figs., 1 tab.

  16. Tactic response of bacteria to zero-valent iron nanoparticles.

    PubMed

    Ortega-Calvo, José-Julio; Jimenez-Sanchez, Celia; Pratarolo, Paolo; Pullin, Huw; Scott, Thomas B; Thompson, Ian P

    2016-06-01

    The microbial assessment of pollutant toxicity rarely includes behavioral responses. In this study, we investigated the tactic response of Pseudomonas putida G7, a representative of soil bacterium, towards engineered zero-valent iron nanoparticles (nZVIs), as a new end-point assessment of toxicity. The study integrated the characterization of size distribution and charge of nZVIs and tactic reaction response by means of inverted capillary assay and computer-assisted motion analysis of motility behavior. Iron nanoparticles (diameter ≤ 100 nm) were prepared in the absence of oxygen to prevent aggregation, and then exposed in aerobic conditions. We first demonstrate that iron nanoparticles can elicit a negative tactic response in bacteria at low but environmentally-relevant, sub-lethal concentrations (1-10 μg/L). Cells were repelled by nZVIs in the concentration gradients created inside the capillaries, and a significant increase in turning events, characteristic of negative taxis, was detected under exposure to nZVIs. These tactic responses were not detectable after sustained exposure of the nanoparticles to oxygen. This new behavioral assessment may be prospected for the design of sensitive bioassays for nanomaterial toxicity. PMID:26967351

  17. Electrochemical depassivation of zero-valent iron for trichloroethene reduction.

    PubMed

    Chen, Liang; Jin, Song; Fallgren, Paul H; Swoboda-Colberg, Norbert G; Liu, Fei; Colberg, Patricia J S

    2012-11-15

    Permeable reactive barriers (PRBs) composed of zero-valent iron (ZVI) are susceptible to passivation, resulting in substantially decreased rates of chlorinated solvent removal over time. In this study, the application of low electrical direct current (DC) to restore the reductive capacity of passivated ZVI was examined. Electrical current was applied to a laboratory column reactor filled with a mixture of pre-passivated ZVI and sand. Variable voltage settings (0-12 V) were applied through two stainless steel electrodes placed at the ends of the reactor. While only partial restoration of the reductive capacity of the passivated ZVI was observed, higher rates of trichloroethene (TCE) removal were always obtained when current was applied, and the rates of TCE removal were roughly proportional to the voltage level. Although differences were observed between the rates and extent of TCE removal within the column, it is noteworthy that TCE removal was not restricted to that region of the column where the electrons entered (i.e., at the cathode). While complete "depassivation" of ZVI may be difficult to achieve in practice, the application of DC demonstrated observable restoration of reactivity of the passivated ZVI. This study provides evidence that this approach may significantly extend the life of a ZVI PRB. PMID:23009798

  18. Zero-valent iron colloid emplacement in sand columns

    SciTech Connect

    Cantrell, K.J.; Kaplan, D.I.

    1997-05-01

    Application of chemically reactive barriers to mitigate contaminant migration is an active area of research and development. Studies were conducted to evaluate a novel approach of emplacing chemically reactive barriers composed of zero-valent iron (Fe{sup 0}) by injecting suspensions of colloidal-size Fe{sup 0} particles into porous media. The specific objective of this study was to evaluate the effect of influent colloid concentration, rate, and volume of colloidal suspensions on Fe{sup 0} colloid emplacement in sand columns. Relatively even distributions of Fe{sup 0} throughout a sand column were obtained at low influent colloid concentrations and high injection rates. As the concentration of influent suspensions was increased, a point was reached beyond which a significant increase in the filtration of Fe{sup 0} particles near the front of the column was observed. This point was also found to occur at lower influent colloid concentrations as the injection rate was decreased, i.e., there was an interactive effect of influent colloid concentration and injection rate on the extent of filtration that occurred near the front of the column. As the volume of the colloidal suspension injected into the column was increased, the distribution of Fe{sup 0} colloids within the column became increasingly even.

  19. Microbiological characteristics in a zero-valent iron reactive barrier

    SciTech Connect

    Gu, Baohua; Watson, David B; Wu, Liyou; Phillips, Debra Helen; White, David C.; Zhou, Jizhong

    2002-01-01

    Zero-valent iron (Fe{sup 0})-based permeable reactive barrier treatment has been generating great interest for passive groundwater remediation, yet few studies have paid particular attention to the microbial activity and characteristics within and in the vicinity of the Fe{sup 0}-barrier matrix. The present study was undertaken to evaluate the microbial population and community composition in the reducing zone of influence by Fe{sup 0} corrosion in the barrier at the Oak Ridge Y-12 Plant site. Both phospholipid fatty acids and DNA analyses were used to determine the total microbial population and microbial functional groups, including sulfate-reducing bacteria, denitrifying bacteria, and methanogens, in groundwater and soil/iron core samples. A diverse microbial community was identified in the strongly reducing Fe{sup 0} environment despite a relatively high pH condition within the Fe{sup 0} barrier (up to pH {approx} 10). In comparison with those found in the background soil/groundwater samples, the enhanced microbial population ranged from {approx} 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. In addition, microbial community composition appeared to change overtime, and the bacterial types of microorganisms increased consistently as the barrier aged. DNA analysis indicated the presence of sulfate-reducing and denitrifying bacteria in the barrier and its surrounding soil. However, the activity of methanogens was found to be relatively low, presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidence of a diverse microbial population within and in the vicinity of the iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevity and enduring efficiency of the Fe{sup 0} barriers are yet

  20. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    SciTech Connect

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul

    2004-03-31

    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  1. Textile dye degradation using nano zero valent iron: A review.

    PubMed

    Raman, Chandra Devi; Kanmani, S

    2016-07-15

    Water soluble unfixed dyes and inorganic salts are the major pollutants in textile dyeing industry wastewater. Existing treatment methods fail to degrade textile dyes and have limitations too. The inadequate treatment of textile dyeing wastewater is a major concern when effluent is directly discharged into the nearby environment. Long term disposal threatens the environment, which needs reclamation. This article reviews the current knowledge of nano zero valent iron (nZVI) technique in the degradation of textile dyes. The application of nZVI on textile dye degradation is receiving great attention in the recent years because nZVI particles are highly reactive towards the pollutant, less toxic, and economical. The nZVI particles aggregate quickly with respect to time and the addition of supports such as resin, nickel, zinc, bentonite, biopolymer, kaolin, rectorite, nickel-montmorillonite, bamboo, cellulose, biochar, graphene, and clinoptilolite enhanced the stability of iron nanoparticles. Inclusion of supports may in turn introduce additional toxic pollutants, hence green supports are recommended. The majority of investigations concluded dye color removal as textile dye compound removal, which is not factual. Very few studies monitored the removal of total organic carbon and observed the products formed. The results revealed that partial mineralization of the textile dye compound was achieved. Instead of stand alone technique, nZVI can be integrated with other suitable technique to achieve complete degradation of textile dye and also to treat multiple pollutants in the real textile dyeing wastewater. It is highly recommended to perform more bench-scale and pilot-scale studies to apply this technique to the textile effluent contaminated sites. PMID:27115482

  2. 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

  3. Reductive dechlorination of chlorinated solvents by zero-valent iron, iron oxide and iron sulfide minerals

    SciTech Connect

    Sivavec, T.M.; Horney, D.P.

    1996-10-01

    The degradation of chlorinated solvents by reduction at the surface of zero-valent metals and bimetallic systems has emerged as an important approach to the in-situ remediation of ground water. Reduction by iron metal was studied in batch and column systems to develop a mechanistic understanding of the reaction chemistry and to determine the factors that affect dechlorination rate and long term performance in field applications.

  4. EFFECTS OF PH ON DECHLORINATION OF TRICHLOROETHYLENE BY ZERO-VALENT IRON

    EPA Science Inventory

    The reduction rates of trichloroethylene (TCE) using zero-valent iron (ZVI) and the rates of iron hydrolysis were characterized at pH values of 5 to 10. The reduction of TCE by ZVI was carried out in batch reactors filled with pH-buffered (phosphate based) solutions under anaerob...

  5. Effect of Zero-Valent Iron on Removal of Escherichia coli O157:H7 from Agricultural Waters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel water filtration system using zero-valent iron (ZVI) is being investigated as a simple and inexpensive approach to reducing E. coli O157:H7 in water for both pre- and post-harvest processes. Purpose: This study was initiated to determine the effectiveness of zero-valent iron in the removal ...

  6. REMOVAL OF HIGH-LEVEL ARSENIC BY ZERO-VALENT IRON

    EPA Science Inventory

    The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the st...

  7. GROUND WATER REMEDIATION OF CHROMIUM USING ZERO-VALENT IRON IN A PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    A series of laboratory experiments were performed to elucidate the chromium transformation and precipitation reactions caused by the corrosion of zero-valent iron in water-based systems. Reaction rates were determined for chromate reduction in the presence of different types of ...

  8. Abiotic remediation of nitro-aromatic groundwater contaminants by zero-valent iron

    SciTech Connect

    Agrawal, A.; Tratnyek, P.G.

    1994-03-18

    Recent laboratory and field experiments have shown that some halogenated hydrocarbons undergo rapid reductive dehalogenation with zero-valent iron and the application of this process is being developed for in-situ remediation of contaminated groundwater. However, from can also reduce other organic substances and is commonly used to synthesize reduction products nitro compounds.

  9. Analytical Characterisation of Nanoscale Zero-Valent Iron: A Methodological Review

    EPA Science Inventory

    Zero-valent iron nanoparticles (nZVI) have been widely tested as they are showing significant promise for environmental remediation. However, many recent studies have demonstrated that their mobility and reactivity in subsurface environments are significantly affected by their te...

  10. LABORATORY EVALUATION OF ZERO-VALENT IRON TO TREAT WATER IMPACTED BY ACID MINE DRAINAGE

    EPA Science Inventory

    This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simu...

  11. ZERO VALENT IRON AND PYRITE SYSTEM USED TO DE-CHLORINATE TOXAPHENE-CONTAMINATED SOILS

    EPA Science Inventory

    The project consisted of a preliminary laboratory study; an outdoor bench scale study and an in situ field Pilot Study to which the zero valent iron and pyrite system (ZVI system) was applied. Several beakers were filled with contaminated soil, the ZVI system and a solvent then...

  12. REDUCTION OF AZO DYES WITH ZERO-VALENT IRON. (R827117)

    EPA Science Inventory

    The reduction of azo dyes by zero-valent iron metal (Fe0) at pH 7.0 in 10 mM HEPES buffer was studied in aqueous, anaerobic batch systems. Orange II was reduced by cleavage of the azo linkage, as evidenced by the production of sulfanilic acid (a substituted ani...

  13. Zero Valent Iron: Impact of Anions Present during Synthesis on Subsequent Nanoparticle Reactivity

    SciTech Connect

    Moore, Kirsten; Forsberg, Brady; Baer, Donald R.; Arnold, William A.; Penn, R. Lee

    2011-10-01

    Zero-valent iron particles are an effective remediation technology for groundwater contaminated with halogenated organic compounds. In particular, nano-scale zero-valent iron is a promising material for remediation due to its high specific surface area, which results in faster rate constants and more effective use of the iron. An aspect of iron nanoparticle reactivity that has not been explored is the impact of anions present during iron metal nanoparticle synthesis. Solutions containing chloride, phosphate, sulfate, and nitrate anions and ferric ions were used to generate iron oxide nanoparticles. The resulting materials were dialyzed to remove dissolved byproducts and then dried and reduced by hydrogen gas at high temperature. The reactivity of the resulting zero valent iron nanoparticles was quantified by monitoring the kinetics as well as products of carbon tetrachloride reduction, and significant differences in reactivity and chloroform yield were observed. The reactivity of nanoparticles prepared in the presence of sulfate and phosphate demonstrated the highest reactivity and chloroform yield. Furthermore, substantial variations in the solid-state products of oxidation (magnetite, iron sulfide, and goethite, among others) were also observed.

  14. Ground water remediation of chromium using zero-valent iron in a permeable reactive barrier

    SciTech Connect

    Puls, R.W.; Powell, R.M.; Paul, C.J.; Blowes, D.

    1998-09-01

    A series of laboratory experiments were performed to elucidate the chromium transformation and precipitation reactions caused by the corrosion of zero-valent iron in water-based systems. Reaction rates were determined for chromate reduction in the presence of different types of iron and in systems with iron mixed with aquifer materials. Various geochemical parameters were measured to confirm the proposed reactions. Laboratory experiments were scaled up to pilot and full-scale field demonstrations. Intensive geochemical sampling in the field tests corroborate laboratory results and successfully demonstrate the effectiveness of this innovative in situ approach to remediate chromate-contaminated ground water using a permeable reactive barrier composed of zero-valent iron.

  15. Comparison of characteristics of montmorillonite supported nano zero valent iron (M-nZVI) and nano zero valent iron (nZVI)

    NASA Astrophysics Data System (ADS)

    How, Ho Kuok; Wan Zuhairi W., Y.

    2015-09-01

    In this study, synthesized montmorillonite supported nano zero valent iron (M-nZVI) and nano zero valent iron (nZVI) are compared physically and chemically. The samples were prepared using chemical reduction method that includes sodium borohydride and ethanol. Due to the tendency of nZVI to aggregate, montmorillonite is used as a supporting material. TEM and FESEM images show that the M-nZVI has decreased the aggregation by dispersing the particles on the surface of montmorillonite whereas images of nZVI show chain-like particle due to aggregation. Both images also show particles synthesized are nanoparticles. With less aggregation, the surface area of the M-nZVI is greater than nZVI which is 45.46 m2/g and 10.49 m2/g respectively. XRD patterns have shown Fe0 are synthesized and small amount of iron oxides are produced. M-nZVI has the capability in reducing aggregation which might lead to the increase in reactivity of the particles thus enhancing the performance of nZVI.

  16. Sorption of PCE in a reactive zero-valent iron system

    SciTech Connect

    Campbell, T.J.; Burris, D.R.

    1995-12-01

    The degradation of the chlorinated solvents perchloroethylene (PCE) and trichloroethylene (TCE) by reduction on the surface of zero-valent iron has emerged in recent years as a potentially viable approach to the remediation of chlorinated solvent-contaminated groundwaters. The sorption of PCE in a batch reactive zero-valent iron system was examined in this study. Aqueous PCE concentrations and total system PCE masses were determined in batch time-series experiments used to ascertain degradation kinetics. Sorbed concentrations were calculated using the difference between the aqueous phase and total system masses. The results showed Langmuir isotherm behavior which is consistent with a model of a finite number of available sorption sites. The kinetics of sorption could not be determined since degradation was also occurring. Knowledge of sorption to reactive and non-reactive sites is of importance in gaining a thorough understanding of the performance-behavior of the flow-through reactive systems envisioned for remediation technologies.

  17. FINAL REPORT. REDUCTION AND IMMOBILIZATION OF RADIONUCLIDES AND TOXIC METAL IONS USING COMBINED ZERO VALENT IRON AND ANAEROBIC BACTERIA

    EPA Science Inventory

    The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. An exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes ...

  18. Zero-valent iron removal rates of aqueous Cr(VI) measured under flow conditions

    SciTech Connect

    Kaplan, Daniel I.; Gilmore, Tyler J.

    2004-06-30

    The rates of Cr(VI) removal from the aqueous phase by zero-valent iron Fe(0) was measured under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a gournwater remediation technology that replaces the sand in a filter pack of a conventioanl well with a reactive material, such as Fe(0).

  19. Environmental application and ecological significance of nano-zero valent iron.

    PubMed

    Yirsaw, Biruck D; Megharaj, Mallavarapu; Chen, Zuliang; Naidu, Ravi

    2016-06-01

    Toxicity studies considering both the bare and stabilized forms of zero valent iron nanoparticles (nZVI) could be timely, given that ecological risks identified are minimized through modification or with substitution of approaches in the synthesis, development and environmental application of the nanoparticles before succeeding to volume production. This review is focused on the fate, transport and toxicological implications of the bare nZVI and surface modified particles used for environmental applications. PMID:27266305

  20. EFFECTS OF PH ON DECHLORINATION OF TRICHLOROETHYLENE BY ZERO-VALENT IRON

    EPA Science Inventory

    The surface normalized reaction rate constants (ksa) of trichloroethylene (TCE) and zero-valent iron (ZVI) was quantified in batch reactors at pH values between 1.7 and 10. The ksa of TCE linearly decreased from 0.044 to 0.009 L/hr-m2 between pH 3.8 and 8.0, whereas the ksa at pH...

  1. Quantitative evaluation of pathways involved in trichloroethylene reduction by zero-valent metals: Iron and zinc

    SciTech Connect

    Arnold, W.; Roberts, A.L.; Burris, D.R.; Campbell, T.J.

    1995-12-31

    In order to design in situ remediation systems using zero-valent metals, the mechanism and kinetics of chlorinated solvent degradation by zero-valent metals need clarification. These issues are addressed by conducting detailed investigations of the pathways involved in trichloroethylene (TCE) reduction by two zero-valent metals. Analyses are based on batch reaction data for chloroethylene reduction by iron and zinc. Experiments were conducted using TCE and each readily available reaction product of TCE degradation as a starting material and monitoring the disappearance of the parent chemical and the appearance of reaction products over time. Models were developed by working backwards through the hypothesized reaction sequence. Determining rate constants for the latter steps in the pathway, inserting them into the more complex models for more highly oxidized compounds, and obtaining rate constants for the remaining steps in the transformation of the oxidized species was repeated until a model for trichloroethylene was developed. Results indicate that reactions may not occur via a process of sequential hydrogenolysis or hydrogenation. Ethylene and/or ethane production are too rapid to be accounted for in this manner. The product distribution, especially the presence of acetylene, can only be explained by invoking reductive elimination reactions.

  2. In situ remediation of chromium contaminated groundwater using zero valent iron

    SciTech Connect

    Blowes, D.W.; Ptacek, C.J.; Hanton-Fong, C.J.; Jambor, J.L.

    1995-12-01

    In situ porous reactive walls, using zero-valent iron as a reductant, are an alternative technology for the treatment of groundwater contaminated with electroactive elements, such as Cr(VI). Laboratory column and batch experiments were conducted to assess the treatment of Cr(VI) using zero-valent iron in the form of iron filings. Batch tests were conducted with and without calcite addition. Batch test results indicate that removal using iron filings is rapid, with initial Cr(VI) concentrations reduced from approximately 20 mg/L to < 0.05 mg/L within 3 hours. Iron filings retained from the batch tests were examined mineralogically. The results indicate that the most abundant secondary minerals are goethite, lepidocrocite, maghemite and hematite. Of these minerals, the most abundant was goethite. No discrete chromium-bearing phases were detected, but chromium-rich zones, containing up to 27.3 wt.% Cr as Cr(OH){sub 3}, were detected within the iron oxyhydroxides, most notably within the goethite. A flow-through column experiment, conducted at a flow rate of 10 m/a indicated continuing treatment of Cr(VI) at concentrations of approximately 20 mg/L to <0.05 mg/L for more than 130 pore volumes.

  3. Synthesis, characterization, and reactivity of cellulose modified nano zero-valent iron for dye discoloration

    NASA Astrophysics Data System (ADS)

    Wang, Xiangyu; Wang, Pei; Ma, Jun; Liu, Huiling; Ning, Ping

    2015-08-01

    Nano zero-valent iron (NZVI) was innovatively and successfully modified by using hydroxyethyl cellulose (HEC) and hydroxypropylmethyl cellulose (HPMC) as dispersants. The systematic characterization observations (including XRD, SEM and TEM) illustrate that, compared with bare nano zero-valent iron particles (BNZVI), the particle sizes of hydroxyethyl cellulose modified (ENZVI) and hydroxypropylmethyl cellulose modified (PNZVI) were decreased, while the dispersity and antioxidizability of ENZVI and PNZVI particles were increased. The discoloration efficiencies of ENZVI, PNZVI, and BNZVI were compared by using dyes (including orange II, methyl orange, methyl blue, and methylene blue) as target pollutant. The results show that both the discoloration efficiency and reaction rate of ENZVI and PNZVI are higher than that of BNZVI. In addition, effects of dispersant content, dye type, pH value, initial dye concentration, iron dosage, and reaction temperature on discoloration efficiencies were studied. The results show that discoloration efficiency was decreased by increasing initial pH value and dye concentration, and it was increased with the increase the iron dosage and reaction temperature. Under optimized NZVI addition of 0.7 g L-1, the discoloration efficiencies of ENZVI and PNZVI were increased to 96.33% and 98.62%, respectively. And the possible discoloration pathway and dispersant modification mechanism of NZVI were discussed. This study suggests hydroxyethyl cellulose and hydroxypropylmethyl cellulose dispersed NZVI can be utilized as a promising modified nano-material for degradation of dye wastewater.

  4. Methods of preparation and modification of advanced zero-valent iron nanoparticles, their properties and application in water treatment technologies

    NASA Astrophysics Data System (ADS)

    Filip, Jan; Kašlík, Josef; Medřík, Ivo; Petala, Eleni; Zbořil, Radek; Slunský, Jan; Černík, Miroslav; Stavělová, Monika

    2014-05-01

    Zero-valent iron nanoparticles are commonly used in modern water treatment technologies. Compared to conventionally-used macroscopic iron or iron microparticles, the using of nanoparticles has the advantages given mainly by their generally large specific surface area (it drives their high reactivity and/or sorption capacity), small dimensions (it allows their migration e.g. in ground water), and particular physical and chemical properties. Following the applications of zero-valent iron particles in various pilot tests, there arose several critical suggestions for improvements of used nanomaterials and for development of new generation of reactive nanomaterials. In the presentation, the methods of zero-valent iron nanoparticles synthesis will be summarized with a special attention paid to the thermally-induced solid-state reaction allowing preparation of zero-valent iron nanoparticles in an industrial scale. Moreover, the method of thermal reduction of iron-oxide precursors enables to finely tune the critical parameters (mainly particle size and morphology, specific surface area, surface chemistry of nanoparticles etc.) of resulting zero-valet iron nanoparticles. The most important trends of advanced nanoparticles development will be discussed: (i) surface modification of nanomaterilas, (ii) development of nanocomposites and (iii) development of materials for combined reductive-sorption technologies. Laboratory testing of zero-valent iron nanoparticles reactivity and migration will be presented and compared with the field observations: the advanced zero-valent iron nanoparticles were used for groundwater treatment at the locality contaminated by chlorinated hydrocarbons (VC, DCE, TCE and PCE) and reacted nanoparticles were extracted from the sediments for their fate assessment. The authors gratefully acknowledge the support by the Technology Agency of the Czech Republic "Competence Centres" (project No. TE01020218) and the EU FP7 (project NANOREM).

  5. Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLs

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  6. Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLS

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  7. Reduction and Immobilization of Radionuclides and Toxic Metal Ions Using Combined Zero Valent Iron and Anaerobic Bacteria

    SciTech Connect

    Lenly J. Weathers; Lynn E. Katz

    2002-05-29

    The use of zero valent iron, permeable reactive barriers (PRBs) for groundwater remediation continues to increase. AN exciting variation of this technology involves introducing anaerobic bacteria into these barriers so that both biological and abiotic pollutant removal processes are functional. This work evaluated the hypothesis that a system combining a mixed culture of sulfate reducing bacteria (SRB) with zero valent iron would have a greater cr(VI) removal efficiency and a greater total Cr(VI) removal capacity than a zero valent iron system without the microorganisms. Hence, the overall goal of this research was to compare the performance of these types of systems with regard to their Cr(VI) removal efficiency and total Cr(VI) removal capacity. Both batch and continuous flow reactor systems were evaluated.

  8. Hybrid biological, electron beam and zero-valent nano iron treatment of recalcitrant metalworking fluids.

    PubMed

    Thill, Patrick G; Ager, Duane K; Vojnovic, Borivoj; Tesh, Sarah J; Scott, Thomas B; Thompson, Ian P

    2016-04-15

    Hybrid approaches for the remediation and detoxification of toxic recalcitrant industrial wastewater were investigated. The focus was waste metalworking fluid, which was selected as a representative model of other waste streams that are toxic, recalcitrant and that require more sustainable routes of safe disposal. The hybrid approaches included biodegradation, electron beam irradiation and zero-valent nano iron advanced oxidation processes that were employed individually and in sequence employing a factorial design. To compare process performance operationally exhausted and pristine metalworking fluid were compared. Sequential hybrid electron beam irradiation, biological, nanoscale zero-valent iron and biological treatment lead to synergistic detoxification and degradation of both recalcitrant streams, as determined by complementary surrogates and lead to overall improved COD removal of 92.8 ± 1.4% up from 85.9 ± 3.4% for the pristine metalworking fluid. Electron beam pre-treatment enabled more effective biotreatment, achieving 69.5 ± 8% (p = 0.005) and 24.6 ± 4.8% (p = 0.044) COD reductions. PMID:26905800

  9. Utilization of food industry wastes for the production of zero-valent iron nanoparticles.

    PubMed

    Machado, S; Grosso, J P; Nouws, H P A; Albergaria, J T; Delerue-Matos, C

    2014-10-15

    The proper disposal of the several types of wastes produced in industrial activities increases production costs. As a consequence, it is common to develop strategies to reuse these wastes in the same process and in different processes or to transform them for use in other processes. This work combines the needs for new synthesis methods of nanomaterials and the reduction of production cost using wastes from citrine juice (orange, lime, lemon and mandarin) to produce a new added value product, green zero-valent iron nanoparticles that can be used in several applications, including environmental remediation. The results indicate that extracts of the tested fruit wastes (peel, albedo and pulp fractions) can be used to produce zero-valent iron nanoparticles (nZVIs). This shows that these wastes can be an added value product. The resulting nZVIs had sizes ranging from 3 up to 300 nm and distinct reactivities (pulp>peel>albedo extracts). All the studied nanoparticles did not present a significant agglomeration/settling tendency when compared to similar nanoparticles, which indicates that they remain in suspension and retain their reactivity. PMID:25089685

  10. Kinetic controls on the performance of remediation technologies based on zero-valent iron

    SciTech Connect

    Tratnyek, P.G.; Scherer, M.M.

    1998-07-01

    The kinetics of dechlorination by zero-valent iron are usually best described by surface-area normalized, pseudo first-order rate constants (k{sub SA}). For input parameters in preliminary design calculations and generalized modeling exercises, typical values of k{sub SA} for the major groundwater contaminants have been obtained by averaging previously published data. These average values of k{sub SA} (k{sub SA}{sup avg})are also appropriate for correlation analysis, which can be used to assess the role that chemical structure plays in determining rates of dechlorination by zero-valent iron. Toward this end, the authors have developed a quantitative structure-activity relationship (QSAR) that relates k{sup avg}{sub SA} to energies of the lowest unoccupied molecular orbital (E{sub LUMO}) for the various chlorinated solvents. The WSAR can be used to predict k{sub SA}'s for compounds for which experimental data are not yet available.

  11. Processes affecting reductive dechlorination of chlorinated solvents by zero-valent iron

    SciTech Connect

    Matheson, L.J.; Tratnyek, P.G.

    1993-12-31

    Zero-valent iron may participate in the reductive dechlorination process by three different mechanisms: direct, electrolytic reduction; reduction by hydrogen produced during the corrosion process; and reduction by dissolved (ferrous) iron that is also produced by corroding iron. The first step of electrolytic reduction is presumably, the transfer of one electron from the metal surface to the organic molecule. This results in an organic anion radical that may then lose a halide anion to give a carbon-centered radical, and oxidized iron, which is eventually released to the solution as Fe{sup 2+}. The goal of this research is to provide a comprehensive survey of the mechanisms that affect the performance of this reactive barrier technology.

  12. Reduced aggregation and sedimentation of zero-valent iron nanoparticles in the presence of guar gum.

    PubMed

    Tiraferri, Alberto; Chen, Kai Loon; Sethi, Rajandrea; Elimelech, Menachem

    2008-08-01

    Injection of nanoscale zero-valent iron (NZVI) is potentially a promising technology for remediation of contaminated groundwaters. However, the efficiency of this process is significantly hindered by the rapid aggregation of the iron nanoparticles. The aim of this study was to enhance the colloidal stability of the nanoparticles through the addition of the "green" polymer guar gum. We evaluated the properties of guar gum and its influence on the surface properties, particle size, aggregation, and sedimentation of iron nanoparticles. Commercial iron nanoparticles were dispersed in guar gum solutions, and their aggregation and sedimentation behaviors were compared to those of bare iron nanoparticles and commercial nanoparticles modified with a biodegradable polymer (polyaspartate). High performance size exclusion chromatography, charge titration, and viscosity assessment showed that guar gum is a high molecular weight polymer which is nearly neutrally charged, rendering it suitable for steric stabilization of the iron nanoparticles. Electrophoretic mobility measurements demonstrated the ability of guar gum to adsorb on the nanoparticles, forming a slightly negatively charged layer. Dynamic light scattering experiments were conducted to estimate the particle size of the different nanoparticle suspensions and to determine the aggregation behavior at different ionic strengths. Guar gum effectively reduced the hydrodynamic radius of the bare nanoparticles from 500 nm to less than 200 nm and prevented aggregation of the nanoparticles even at very high salt concentrations (0.5 M NaCl and 3 mM CaCl(2)). Sedimentation profiles of the different nanoparticle suspensions confirmed the improved stability of the iron nanoparticles in the presence of guar gum. The results strongly suggest that guar gum can be used to effectively deliver stabilized zero-valent iron nanoparticles for remediation of contaminated groundwater aquifers. PMID:18508073

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

    SciTech Connect

    Fogwell, Thomas W.; Santina, Pete

    2013-07-01

    Many DOE remediation sites have chemicals of concern that are compounds in higher oxidation states, which make them both more mobile and more toxic. The chemical reduction of these compounds both prevents the migration of these chemicals and in some cases reduces the toxicity. It has also been shown that zero-valent iron is a very effective substance to use in reducing oxygenated compounds in various treatment processes. These have included the treatment of halogenated hydrocarbons in the form volatile organic compounds used as solvents and pesticides. Zero-valent iron has also been used to reduce various oxidized metals such as chromium, arsenic, and mercury in order to immobilize them, decrease their toxicity, and prevent further transport. In addition, it has been used to immobilize or break down other non-metallic species such as selenium compounds and nitrates. Of particular interest at several DOE remediation sites is the fact that zero-valent iron is very effective in immobilizing several radioactive metals which are mobile in their oxidized states. These include both technetium and uranium. The main difficulty in using zero-valent iron has been its tendency to become inactive after relatively short periods of time. While it is advantageous to have the zero-valent iron particles as porous as possible in order to provide maximum surface area for reactions to take place, these pores can become clogged when the iron is oxidized. This is due to the fact that ferric oxide has a greater volume for a given mass than metallic iron. When the surfaces of the iron particles oxidize to ferric oxide, the pores become narrower and will eventually shut. In order to minimize the degradation of the chemical activity of the iron due to this process, a modification of zero-valent iron has been developed which prevents or slows this process, which decreases its effectiveness. It is called sulfur-modified iron, and it has been produced in high purity for applications in

  14. Enhanced reduction of nitrate by supported nanoscale zero-valent iron prepared in ethanol-water solution.

    PubMed

    Park, Heesu; Park, Yong-Min; Oh, Soo-Kyeong; You, Kyoung-Min; Lee, Sang-Hyup

    2009-03-01

    Nanoscale zero-valent iron is famous for its high reactivity originating from its high surface area, and has emerged as an extension of granular zero-valent iron technology. Due to its extremely small size, nanosized iron cannot be used as a medium in a permeable reactive barrier system, which is the most popular application of granular iron. To overcome this shortcoming, supported nanoscale zero-valent iron was created. In addition to this, the preparation solution was modified to enhance the reactivity. An ethanol/water solvent containing a dispersant of polyethylene glycol was used to synthesize nanoscale iron. This preparation was done in the presence of an ion-exchange resin as a supporting material. Nanoscale zero-valent iron was formed and bound to the granular resin at the same time through the borohydride reduction of an iron salt, and the resulting product was compared with that prepared in a conventional way of using water only. Switching the preparation solution increased the supported nanoscale iron's BET surface area and Fe content from 31.63 m2 g(-1) and 18.19 mg Fe g(-1) to 38.10 m2 g(-1) and 22.44 mg Fe g(-1), respectively. Kinetic analysis from batch tests revealed that a higher denitrification rate was achieved by the supported nanoscale zero-valent iron prepared in the modified way. The pseudo-first-order reaction constant of 0.462 h(-1) suggested that the reactivity of the supported iron, prepared in ethanol/water, increased by 61% compared with the one prepared in water. The higher rates of reaction, based on higher specific area and iron content, suggest that this new supported nanoscale iron can be used successfully for permeable reactive barriers. PMID:19438058

  15. Applicability of nano zero valent iron (nZVI) in sono - Fenton process

    NASA Astrophysics Data System (ADS)

    Taha, M. R.; Ibrahim, A. H.; Amat, R. C.; Azhari, A. W.

    2014-04-01

    Fenton process is one of the advanced oxidation processes (AOPs) used to remove complex organic pollutants in wastewater. In this study, instead of iron sulfate (FeSO4), nano zero valent iron (nZVI) was used as a major source of ferrous iron (Fe2+). In order to enhance the process, ultrasound was utilized in this study. Results show that, with the aid of ultrasound, nZVI produced more Fe2+ compared to FeSO4 at pH 2. Furthermore, combination of higher intensity and longer sonication time in Fenton process acceleratde the chemical oxygen demand (COD) removal from palm oil mill effluent (POME). Through the process, 80% of COD content was removed within 2 hours instead of 24 hours of silent degradation.

  16. Dechlorination of 1,2,3-trichloropropane by zero-valent iron

    SciTech Connect

    Focht, R.M.; Gillham, R.W.

    1995-12-01

    This study investigated the dechlorination of aqueous 1,2,3-trichloropropane in the presence of zero-valent iron. Using flow-through column procedures, the rate of dechlorination was significantly enhanced by the presence of iron, with the half life decreasing in proportion to the iron surface area to solution volume ratio. Unlike previous results obtained for chlorinated C{sub 1} and C{sub 2} compounds, half-lives increased significantly over time, at rates ranging from 5.0 to 13.9 minutes per pore volume of water passed through the column. No accumulation of chlorinated products of degradation was detected, and the principal products of degradation were Cl{sup -} and propene. The products of degradation and the trends in pH suggest reductive dechlorination and dehydrochlorination to be the degradation mechanisms.

  17. Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

    PubMed

    Guha, Saumyen; Bhargava, Puja

    2005-01-01

    Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely. PMID:16121509

  18. Zero-valent iron-promoted dechlorination of polychlorinated biphenyls (PCBs)

    SciTech Connect

    Chuang, Fei-Wen; Larson, R.A.

    1995-12-01

    Zero-valent iron promoted the dechlorination of PCBs (Aroclors 1221 and 1254) at elevated temperatures in an oxygen-limited environment. At temperatures higher than 300{degrees}C, dechlorination of Aroclor 1221 began to occur; at 400{degrees}C, the major reaction product, biphenyl, was observed in highest yield. (At this temperature most of the PCBs were dechlorinated to biphenyl within 10 min.) At temperatures of 500{degrees}C or higher, dechlorination and other reactions of PCBs took place. At 600{degrees}C, almost all PCBs were destroyed by reactions other than hydrogenolytic dechlorination. Similar reactions were observed with the more highly chlorinated Aroclor 1254. Water or other impurities associated with the iron surface may donate protons or hydrogen atoms to the PCBs and take part in other reactions.

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

    PubMed Central

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

    2015-01-01

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

  20. Remediating RDX-contaminated water and soil using zero-valent iron

    SciTech Connect

    Singh, J.; Comfort, S.D.; Shea, P.J.

    1998-09-01

    Soil and water contaminated with RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) pose a serious threat to the environment and human health. The objective was to determine the potential for using zero-valent iron (Fe{sup 0}) to remediate RDX-contaminated water and soil. Mixing an aqueous solution of 32 mg RDX L{sup {minus}1} (spiked with {sup 14}C-labeled RDX) with 10 g Fe{sup 0} L{sup {minus}1} resulted in complete RDX destruction within 72 h. Nitroso derivatives of RDX accounted for approximately 26% of the RDX transformed during the first 24 h; these intermediates disappeared within 96 h ad the remaining {sup 14}C products were water soluble and not strongly sorbed by iron surfaces. When RDX-contaminated soil was treated with a single amendment of Fe{sup 0} in a static soil microcosm, more than 60% of the initial {sup 14}C-RDX was recovered as {sup 14}CO{sub 2} after 112 d. Treating surface and subsurface soils containing 3,600 mg RDX kg{sup {minus}1} with 50 g Fe{sup 0} kg{sup {minus}1} at a constant soil water content resulted in a 52% reduction in extractable RDX following 12 mo of static incubation. A second Fe{sup 0} addition at 12 mo further reduced the initial extractable RDX by 71% after 15 mo. These results support the use of zero-valent iron for in situ remediation of RDX-contaminated soil.

  1. USE OF PRETREATMENT ZONES AND ZERO-VALENT IRON FOR THE REMEDIATION OF CHLOROALKENES IN AN OXIC AQUIFER

    EPA Science Inventory

    Pre-treatment zones (PTZs) composed of sand, 10% zero-valent iron [Fe(0)]/sand, and 10% pyrite (FeS2)/sand were examined for their ability to prolong Fe(0) reactivity in aboveground column reactors and a subsurface permeable reactive barrier (PRB). The test site had an acidic, o...

  2. LONG-TERM PERFORMANCE OF PERMEABLE REACTIVE BARRIERS USING ZERO-VALENT IRON: GEOCHEMICAL AND MICROBIOLOGICAL EFFECTS

    EPA Science Inventory

    Geochemical and microbiological factors that control long-term performance of subsurface permeable reactive barriers were evaluated at the Elizabeth City, NC and the Denver Federal Center, CO sites. These ground water treatment systems use zero-valent iron filings (Peerless Meta...

  3. The use of zero-valent iron filtration to reduce Escherichia coli and Listeria innocua in irrigation water

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Introduction: Irrigation water can be a source of contamination in outbreaks associated with produce. Zero-valent iron (ZVI) filtration has been effective in E. coli O157:H12 in irrigation water, but has not been evaluated against Listeria spp. Purpose: To 1) determine effectiveness of ZVI filters...

  4. Partial oxidation (“aging”) and surface modification decrease the toxicity of nano-sized zero valent iron.

    EPA Science Inventory

    Nanosize zero-valent iron (nZVI) is used as a redox-active catalyst for in situ remediation of contaminated ground waters. In aqueous environments, nZVI oxidizes over time (i.e., “ages”) to magnetite and other oxides. For remediation, hi...

  5. Injection of Zero Valent Iron into an Unconfined Aquifer Using Shear-Thinning Fluids

    SciTech Connect

    Truex, Michael J.; Vermeul, Vincent R.; Mendoza, Donaldo P.; Fritz, Brad G.; Mackley, Rob D.; Oostrom, Martinus; Wietsma, Thomas W.; Macbeth, Tamzen

    2011-02-18

    Approximately 190 kg of two micron-diameter zero-valent iron (ZVI) particles were injected into a test zone in the top two meters of an unconfined aquifer within a trichloroethene (TCE) source area. A shear-thinning fluid was used to enhance ZVI delivery in the subsurface to a radial distance of up to four meters from a single injection well. The ZVI particles were mixed in-line with the injection water, shear-thinning fluid, and a low concentration of surfactant. ZVI was observed at each of the seven monitoring wells within the targeted radius of influence during injection. Additionally, all wells within the targeted zone showed low TCE concentrations and primarily dechlorination products present 44 days after injection. These results suggest that ZVI can be directly injected into an aquifer with shear-thinning fluids and extends the applicability of ZVI to situations where other emplacement methods may not be viable.

  6. Remediation of hexavalent chromium contaminated soil by biochar-supported zero-valent iron nanoparticles.

    PubMed

    Su, Huijie; Fang, Zhanqiang; Tsang, Pokeung Eric; Zheng, Liuchun; Cheng, Wen; Fang, Jianzhang; Zhao, Dongye

    2016-11-15

    In this study, a kind of high-efficiency and low-cost biochar-supported zero-valent iron nanoparticles (nZVI@BC) was synthesised and used in the remediation of Cr(VI)-contaminated soil. The remediation tests indicated that the immobilisation efficiency of Cr(VI) and Crtotal was 100% and 91.94%, respectively, by 8g nZVI@BC per kg soil for 15 d of remediation. Further investigations showed that exchangeable Cr was almost completely converted to Fe-Mn oxides and organic matter. Moreover, nZVI@BC could effectively improve soil fertility and reduce the leachability of Fe caused by nZVI. At the same time, the cabbage mustard growth experiments indicated that the phytotoxicity of Cr(VI) and Fe in the seedlings was effectively decreased by nZVI@BC treatment, and that the cabbage mustard growth was enhanced. PMID:27469041

  7. 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. PMID:23107289

  8. Zero-valent iron for the removal of soluble uranium in simulated DOE site groundwater

    SciTech Connect

    Bostick, W.D.; Jarabek, R.J.; Fiedor, J.N.

    1997-12-31

    Groundwater at the Bear Creek Valley Characterization Area, located at the Oak Ridge Y-12 Plant, is contaminated with regulated metals and volatile organic compounds (VOCs) due to former site activities and disposal practices. The contaminant of principle concern, from the perspective of protecting human health, is soluble uranium, which is present in some waters at concentrations up to a few parts-per-million. We present product speciation and relative reaction kinetics; for removal of soluble uranium under oxic and anoxic conditions with use of zero-valent iron. Under oxic conditions, U(VI) is rapidly and strongly sorbed to hydrous ferric oxide particulate ({open_quotes}rust{close_quotes}), whereas uranium is slowly and incompletely reduced to U(IV) under anoxic conditions.

  9. Installation of a subsurface groundwater treatment wall composed of granular zero-valent iron

    SciTech Connect

    Yamane, C.L.; Warner, S.D.; Gallinatti, J.D.

    1995-12-01

    A subsurface treatment wan (consisting of granular, zero-valent iron and gravel) and low-permeability slurry wall system was installed as the final remedy at a former semiconductor manufacturing facility in the south San Francisco Bay area. The property has been vacant since 1983, and the former facility`s lease recently expired. This treatment wall replaced a groundwater pump and treat system that was installed as an interim remedy in 1987. While the pump and treat system may have been acceptable to regulatory agencies as a final site remedy, the treatment wall was proposed and eventually selected as the final remedy because it would eliminate above-ground treatment systems on the property and thereby have little to no effect on the property`s future use; it would eliminate the necessity for weekly operation and maintenance and therefore avoid access issues that might arise after the tenant`s lease expired; and it would greatly reduce total remediation costs.

  10. Enhancement of aerobic granulation by zero-valent iron in sequencing batch airlift reactor.

    PubMed

    Kong, Qiang; Ngo, Huu Hao; Shu, Li; Fu, Rong-Shu; Jiang, Chun-Hui; Miao, Ming-sheng

    2014-08-30

    This study elucidates the enhancement of aerobic granulation by zero-valent iron (ZVI). A reactor augmented with ZVI had a start-up time of aerobic granulation (43 days) that was notably less than that for a reactor without augmentation (64 days). The former reactor also had better removal efficiencies for chemical oxygen demand and ammonium. Moreover, the mature granules augmented with ZVI had better physical characteristics and produced more extracellular polymeric substances (especially of protein). Three-dimensional-excitation emission matrix fluorescence showed that ZVI enhanced organic material diversity. Additionally, ZVI enhanced the diversity of the microbial community. Fe(2+) dissolution from ZVI helped reduce the start-up time of aerobic granulation and increased the extracellular polymeric substance content. Conclusively, the use of ZVI effectively enhanced aerobic granulation. PMID:25108827

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  12. Multicomponent reactive transport in an in situ zero-valent iron cell

    SciTech Connect

    Yabusaki, Steven B. ); Cantrell, Kirk J. ); Sass, Bruce; Steefel, Carl

    2000-12-01

    Data collected from a field study of in situ zero-valent iron treatment for TCE were analyzed in the context of coupled transport and reaction processes. The focus of this analysis was to understand the behavior of chemical components, including contaminants, in groundwater transported through the iron cell of a pilot-scale funnel and gate treatment system. A multicomponent reactive transport simulator was used to simultaneously model mobile and nonmobile components undergoing equilibrium and kinetic reactions including TCE degradation, parallel iron dissolution reactions, precipitation of secondary minerals, and complexation reactions. The resulting mechanistic model of coupled processes reproduced solution chemistry behavior observed in the iron cell with a minimum of calibration. These observations included the destruction of TCE and cis-1,2-DCE; increases in pH and hydrocarbons; and decreases in EH, alkalinity, dissolved O2 and CO2, and major ions (i.e., Ca, Mg, Cl, sulfate, nitrate). Mineral precipitation in the iron zone was critical to correctly predicting these behaviors. The dominant precipitation products were ferrous hydroxide, siderite, aragonite, brucite, and iron sulfide. In the first few centimeters of the reactive iron cell, these precipitation products are predicted to account for a 3% increase in mineral volume per year, which could have implications for the longevity of favorable barrier hydraulics and reactivity. The inclusion of transport was key to understanding the interplay between rates of transport and rates of reaction in the field.

  13. Trichloroethene Reduction within a Nonaqueous Phase Liquid using Zero Valent Iron

    NASA Astrophysics Data System (ADS)

    Berge, N. D.; Ramsburg, C. A.

    2008-12-01

    The application of reactive slurries or suspensions (usually of reactive zero valent iron particles) is being considered for treatment of dense non-aqueous phase liquid (DNAPL) source zones. Effective treatment of NAPL source zones with reactive particles requires delivery of particles within the vicinity of the NAPL. To date, iron-mediated remediation technologies rely on the use of aqueous-based particle suspensions. When utilizing these aqueous-based suspensions of reactive iron particles, contaminant transformation is dependent on dissolution of contaminants from the DNAPL prior to reaction. The reliance upon dissolution kinetics may introduce a rate limitation during treatment of DNAPL source zones with aqueous-based reactive slurries. Incorporation of the reactive particles into the NAPL (i.e., reduction occurring within the NAPL) may alleviate any dissolution limitation associated with aqueous-based reactive slurries. This exploratory research evaluated the feasibility of creating iron-mediated TCE reduction within a NAPL. Emphasis was placed on elucidating the role of water in the reductive dechlorination process when it occurs within a NAPL. Batch experiments were conducted in 125 mL reactors containing iron particles and NAPLs of various composition under an argon atmosphere. For these proof-of-concept experiments, NAPL mixtures were designed to ensure initial TCE concentration was constant. Results suggest that iron-mediated reactions within chlorinated ethene DNAPLs are feasible, though the viability of controlling both the iron content and chemistry of DNAPL located within the subsurface remains unknown.

  14. Reduction of 1,2-dibromoethane in the presence of zero-valent iron

    SciTech Connect

    Rajagopal, V.K.; Burris, D.R.

    1999-08-01

    The degradation reaction of 1,2-dibromoethane (ethylene dibromide or EDB) in water was studied in the presence of zero-valent iron (acid-cleaned, cast iron) in well-mixed batch aqueous systems. The observed products were ethylene and bromide ions. Carbon and bromine mass recoveries of >95% were obtained. Bromoethane and vinyl bromide were not observed. The reduction rates of bromoethane and vinyl bromide with iron indicate that they should have been observed if they were significant reaction intermediates for EDB. The results indicate that reductive {beta}-elimination may be the dominant reaction pathway. Reaction kinetics are rapid and pseudo-first order. The activation energy was determined to be 50 kJ/mol, indicating that the reaction rate may not be aqueous phase diffusion controlled but rather controlled by the chemical reaction rate on the iron surface. Metallic iron may be a suitable treatment approach for EDB-contaminated groundwater in above-ground, as well as in situ applications, due to rapid kinetics and nontoxic products.

  15. Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

    SciTech Connect

    Wu, Yuxin; Versteeg, R.; Slater, L.; LaBrecque, D.

    2009-06-01

    Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO{sub 3} and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO{sub 3} as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO{sub 3} dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO{sub 3} forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO{sub 3} precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

  16. 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

  17. Remediation of soil contaminated with pyrene using ground nanoscale zero-valent iron.

    PubMed

    Chang, Ming-Chin; Shu, Hung-Yee; Hsieh, Wen-Pin; Wang, Min-Chao

    2007-02-01

    The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-valent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data. PMID:17355083

  18. Remediation of soil contaminated with pyrene using ground nanoscale zero-valent iron

    SciTech Connect

    Ming-Chin Chang; Hung-Yee Shu; Wen-Pin Hsieh; Min-Chao Wang

    2007-02-15

    The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-valent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data. 19 refs., 9 figs., 2 tabs.

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

    SciTech Connect

    Johnson, R. L.; Thoms, R. B.; Johnson, R. O.; Nurmi, J. T.; Tratnyek, Paul G.

    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, at 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.

  20. Enhancing zero valent iron based natural organic matter removal by mixing with dispersed carbon cathodes.

    PubMed

    Liu, Peng; Keller, Jurg; Gernjak, Wolfgang

    2016-04-15

    Former studies have shown that adding granular activated carbon (GAC) cathodes could enhance the overall performance of the zero valent iron (ZVI) process for organics removal. The present study evaluates for the first time the performance of such an enhanced ZVI process to remove natural organic matter (NOM), an important water quality parameter in drinking water. Lab-scale batch tests were conducted with surface reservoir feed water from a drinking water plant. In the GAC enhanced ZVI process dissolved organic carbon (DOC) and UV254 were reduced by 61±3% and 70±2%, respectively, during 24h treatment corresponding to 1.8min empty bed contact time. The process was superior to ZVI alone, particularly during the earlier stages of the process due to the synergistically increased iron dissolution rate. Besides GAC, graphite and anthracite also prove to be suitable and potentially more cost-effective options as cathode materials for the enhanced ZVI process, whereby electrically conductive graphite clearly outperformed anthracite. The dominant mechanisms in terms of NOM removal from surface water were found to be coagulation following iron dissolution and adsorption in the case of employing GAC. Oxidation was also occurring to a lesser degree, converting some non-biodegradable into biodegradable DOC. PMID:26808400

  1. Zero-Valent Iron Permeable Reactive Barriers: A Review of Performance

    SciTech Connect

    Korte, NE

    2001-06-11

    This report briefly reviews issues regarding the implementation of the zero-valent iron permeable reactive barrier (PRB) technology at sites managed by the U.S. Department of Energy (DOE). Initially, the PRB technology, using zero-valent iron for the reactive media, was received with great enthusiasm, and DOE invested millions of dollars testing and implementing PRBs. Recently, a negative perception of the technology has been building. This perception is based on the failure of some deployments to satisfy goals for treatment and operating expenses. The purpose of this report, therefore, is to suggest reasons for the problems that have been encountered and to recommend whether DOE should invest in additional research and deployments. The principal conclusion of this review is that the most significant problems have been the result of insufficient characterization, which resulted in poor engineering implementation. Although there are legitimate concerns regarding the longevity of the reactive media, the ability of zero-valent iron to reduce certain chlorinated hydrocarbons and to immobilize certain metals and radionuclides is well documented. The primary problem encountered at some DOE full-scale deployments has been an inadequate assessment of site hydrology, which resulted in misapplication of the technology. The result is PRBs with higher than expected flow velocities and/or incomplete plume capture. A review of the literature reveals that cautions regarding subsurface heterogeneity were published several years prior to the full-scale implementations. Nevertheless, design and construction have typically been undertaken as if the subsurface was homogeneous. More recently published literature has demonstrated that hydraulic heterogeneity can cause so much uncertainty in performance that use of a passive PRB is precluded. Thus, the primary conclusion of this review is that more attention must be given to site-specific issues. Indeed, the use of a passive PRB requires

  2. Debromination of decabromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron: preparation, characterization and influence factors.

    PubMed

    Pang, Zhihua; Yan, Mengyue; Jia, Xiaoshan; Wang, Zhenxing; Chen, Jianyu

    2014-02-01

    An organo-montmorillonite-supported nanoscale zero-valent iron material (M-NZVI) was synthesized to degrade decabromodiphenyl ether (BDE-209). The results showed that nanoscale zero-valent iron had good dispersion on organo-montmorillonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30-90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased. PMID:25076541

  3. Recent advances and future perspectives of nanosized zero- valent iron for extraction of heavy elements from metallurgical sludges

    NASA Astrophysics Data System (ADS)

    Mikhailov, I. Yu; Levina, V. V.; Kolesnikov, E. A.; Chuprunov, K. O.; Gusev, A. A.; Godymchuk, A. Yu; Kuznetsov, D. V.

    2016-01-01

    Advanced oxidation processes with nanosized zero-valent iron have presented great potential in wastewater treatment technology and now experience both increasing popularity and reliable technical improvements. Besides wastewater treatment, there is another promising application for an emerging technology of iron nanoparticles - as Fenton-like catalyst for extraction of valuable elements from poor and secondary raw materials such as metallurgical sludges. In present research, we carried out a set of experiments with emphasis on the physicochemical mechanisms and their relationship to the performance. In particular, we examined complex acidic - hydrogen peroxide leaching of zinc from blast furnace sludge with nanosized zero-valent iron as Fenton-like catalyst. Results of the experiments showed promising potential for subsequent application in extraction of heavy and rare-earth elements.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  5. Design and evaluation of an in-situ ground water treatment wall composed of zero-valent iron

    SciTech Connect

    Gallinatti, J.D.; Warner, S.D.; Yamane, C.L.; Szerdy, F.S.; Hankins, D.A.; Major, D.W.

    1995-09-01

    An in-situ permeable treatment wall using zero-valent iron for the remediation of ground water affected by chlorinated volatile organic compounds (VOCs) was recently constructed in Sunnyvale, California. Because this site was the first full-scale application of this technology as a final remedy of VOC-affected ground water, it provides a framework for assessing the factors that must be considered when moving from laboratory studies of this treatment technology to design and construction of a full-scale treatment system. Experience from this case study is valuable for both practical design considerations and as incentives for future research. The patented treatment process, licensed by Environmental Technologies Inc., utilizes granular zero-valent iron as a porous medium to enhance the degradation of VOCs dissolved in ground water. The dissolved VOCs, such as 1,1,1-trichloroethylene (TCE), that pass through the granular iron matrix are transformed through the oxidation of the iron and reductive dechlorination of the organic compound to a final end product consisting chiefly of chloride and ethylene. The degradation process appears to be abiotic and half-lifes of the transformations are several orders of magnitude faster in the presence of zero-valent granular iron than observed in the ambient environment.

  6. Transport of nano zero-valent iron supported by mesoporous silica microspheres in porous media.

    PubMed

    Yang, Zhangmei; Qiu, Xinhong; Fang, Zhanqiang; Pokeung, Tsang

    2015-01-01

    Effective in situ remediation of groundwater requires the successful delivery of reactive iron particles through sand. However, the agglomeration of nano zero-valent iron (NZVI) particles limits the migration distance, which inhibits their usefulness. In the study described herein, NZVI supported by mesoporous silica microspheres covered with FeOOH (SiO2@FeOOH@Fe) was synthesized, and its mobility was demonstrated on the basis of transport in porous media. Degradation of decabromodiphenyl ether (BDE209) was more efficient by SiO2@FeOOH@Fe than by 'bare' NZVI. Breakthrough curves and mass recovery showed the mobility of SiO2@FeOOH@Fe in granular media was better than that of bare NZVI. It increased greatly in the presence of natural organic matter (NOM) and decreased when high Ca2+ and Mg2+ concentrations were encountered. Analysis of the transport data on the basis of filtration theory showed diffusion to be the main mechanism for particle removal in silicon sand. Increasing the NOM may decrease agglomeration of the grains of sand, which has a positive effect on the mobility of SiO2@FeOOH@Fe. Presumably, increasing the concentrations of Ca2+ and Mg2+ compresses the diffuse double layer of SiO2@FeOOH@Fe, resulting in a reduction of mobility. PMID:26067499

  7. Effect of phosphate and sediment bacteria on trichloroethylene dechlorination with zero valent iron.

    PubMed

    Min, Jee-Eun; Park, In Sun; Ko, Seokoh; Shin, Won Sik; Park, Jae-Woo

    2009-03-01

    The effects of sediment-isolated bacteria and phosphate on the efficacy of zero valent iron (ZVI) for the dechlorination of trichloroethylene (TCE) were examined in batch experiments. TCE (0.3 mM) and a constant concentration of sediment bacteria were simultaneously exposed to ZVI in the presence of 0 mmol, 15 mmol, and 30 mmol of phosphate. TCE profiles, starting from 0.3 mM to about 0.1 mM, exhibited two-phase of sorption kinetics at all three phosphate concentrations without the sediment bacteria. TCE removal was less and slower with phosphate in the system. With the sediment bacteria, however, more TCE was removed with the sediment bacteria than without it, unlike our initial hypothesis. With the sediment bacteria and phosphate, the concentration of ferrous (0.505 mM) ions was doubled that with phosphate only (0.271 mM). The sediment bacteria in this research, mainly Bacillus sp., could contribute to the long-term stability of ZVI reactivity for dechlorination of TCE in sediment. The sediment bacteria in this research could reduce the iron or chelate the evolved ferrous ions to retain the reducing reactivity of ZVI. PMID:19184703

  8. Benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier.

    PubMed

    Chen, Liang; Liu, Fei; Liu, Yulong; Dong, Hongzhong; Colberg, Patricia J S

    2011-04-15

    This study simulated benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier (ZVI PRB) that reduces trichloroethylene (TCE). The effects of elevated pH (10.5) and the presence of a common TCE dechlorination by product [cis-1,2-dichloroethene (cis-1,2-DCE)] on benzene and toluene biodegradation were evaluated in batch experiments. The data suggest that alkaline pH (pH 10.5), often observed down gradient of ZVI PRBs, inhibits Fe(III)-mediated biotransformation of both benzene and toluene. Removal was reduced by 43% for benzene and 26% for toluene as compared to the controls. The effect of the addition of cis-1,2-DCE on benzene and toluene biodegradation was positive and resulted in removal that was greater than or equal to the controls. These results suggest that, at least for cis-1,2-DCE, its formation may not be toxic to iron-reducing benzene and toluene degrading bacteria; however, for microbial benzene and toluene removal down gradient of a ZVI PRB, it may be necessary to provide pH control, especially in the case of a biological PRB that is downstream from a ZVI PRB. PMID:21316847

  9. Degradation of chloropicrin in the presence of zero-valent iron.

    PubMed

    Pearson, Carrie R; Hozalski, Raymond M; Arnold, William A

    2005-12-01

    Halonitromethanes (HNMs) are a class of halogenated disinfection byproducts formed upon the addition of chlorine to water containing organic matter. Batch experiments were performed to investigate the reaction pathways and kinetics of three HNMs (chloropicrin or trichloronitromethane [TCNM], dichloronitromethane [DCNM], and chloronitromethane [CNM]) with zero-valent iron (Fe0). All three compounds reacted rapidly in the presence of Fe0 (1.8-4.4 g/L) with methylamine (MA) as the final product. The geometric surface area-normalized rate constants decreased with decreasing halogenation: TCNM (301 L/[h-m2]) > DCNM (153 L/(h-m2)) > CNM (45.9 L/[h-m2]). Nitromethane, an intermediate species, rapidly reacted to form MA (302 L/[h-m2]). These reactions all experienced some degree of mass transfer limitation (9-73%). The average carbon and chlorine mass balances for TCNM were >85%, indicating that the major reaction products were recovered. The degradation of TCNM and DCNM proceeded via the parallel reaction pathways of hydrogenolysis and alpha-elimination. For TCNM, 60.7 +/- 8.7% of reaction proceeded via hydrogenolysis and 39.3 +/- 6.4% via alpha-elimination. Knowledge of HNM reaction pathways and kinetics in the presence of Fe0 may be useful for predicting the fate of these compounds in drinking water distribution systems containing cast or ductile iron pipe and for developing treatment systems for HNM removal from water. PMID:16445082

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

    PubMed

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

    2016-05-01

    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. PMID:26808248

  11. Enhanced degradation performances of plate-like micro/nanostructured zero valent iron to DDT.

    PubMed

    Kang, Shenghong; Liu, Shengwen; Wang, Huimin; Cai, Weiping

    2016-04-15

    Micro/nanostructured zero valent iron (MNZVI) is successfully mass-synthesized by ball-milling the industrially-reduced iron powders. The as-prepared MNZVI is plate-like in morphology with about 2-5μm in planar size and 35-55nm in thickness, and ∼16m(2)/g in specific surface area. Such plate-like MNZVI has demonstrated much higher degradation performances to DDT [or 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in the aqueous solution than the commercial ZVI powders under acidic conditions. The MNZVI-induced DDT degradation is also much faster than the previously reported results. The time-dependent DDT removal amount can be described by the pseudo first-order kinetic model. Further experiments have shown that more than 50% of DDT can be mineralized in 20min and the rest is dechlorinated to DDX (the products with less chlorine). It has been revealed that the DDT degradation could be attributed to the acid assisted ZVI-induced mineralization and dechlorination. The mineralization process is dominant during the initial stage within 20min, and the dechlorination is the main reaction in the anaphase of the degradation. This work not only deepens understanding of DDT degradation but also could provide a highly efficient material for the practical treatment of the DDT in a real environment. PMID:26780701

  12. Reduction of nitrate by resin-supported nanoscale zero-valent iron.

    PubMed

    Park, Heesu; Park, Yong-Min; Yoo, Kyoung-Min; Lee, Sang-Hyup

    2009-01-01

    For environmental remediation of a contaminated groundwater, the use of nanosized zero-valent iron (nZVI) represents one of the latest innovative technologies. However, nZVI gets easily agglomerated due to its colloidal characteristics and has limited applications. To overcome this drawback, nZVI was immobilized on a supporting material. In this study, nZVI was formed and bound to ion-exchange resin spheres at the same time through the borohydride reduction of an iron salt. The pore structures and physical characteristics of the supported nZVI were investigated and its reactivity was measured using nitrate. The degradation of nitrate appeared to be a pseudo first-order reaction with the observed reaction rate constant of 0.425 h(-1) without pH control. The reduction process continued but at a much lower rate with a rate constant of 0.044 h(-1). When the simulated groundwater was used to assess the effects of coexisting ions, the rate constant was 0.078 h(-1) and it also reduced to 0.0021 h(-1) in later phase. The major limitation of ZVI use for nitrate reduction is ammonium production. By using a support material with ion-exchange capacity, this problem can be solved. The ammonium was not detected in our batch tests. PMID:19494454

  13. Perchlorate reduction by autotrophic bacteria in the presence of zero-valent iron.

    PubMed

    Yu, Xueyuan; Amrhein, Christopher; Deshusses, Marc A; Matsumoto, Mark R

    2006-02-15

    A series of batch experiments were performed to study the combination of zero-valent iron (ZVI) with perchlorate-reducing microorganisms (PRMs) to remove perchlorate from groundwater. In this method, H2 produced during the process of iron corrosion by water is used by PRMs as an electron donor to reduce perchlorate to chloride. Perchlorate degradation rates followed Monod kinetics, with a normalized maximum utilization rate (rmax) of 9200 microg g(-1) (dry wt) h(-1) and a half-velocity constant (Ks) of 8900 microg L(-1). The overall rate of perchlorate reduction was affected by the biomass density within the system. An increase in the OD600 from 0.025 to 0.08 led to a corresponding 4-fold increase of perchlorate reduction rate. PRM adaptation to the local environment and initiation of perchlorate reduction was rapid under neutral pH conditions. At the initial OD600 of 0.015, perchlorate reduction followed pseudo-first-order reaction rates with constants of 0.059 and 0.033 h(-1) at initial pH 7 and 8, respectively. Once perchlorate reduction was established, the bioreductive process was insensitive to the increases of pH from near neutral to 9.0. In the presence of nitrate, perchlorate reduction rate was reduced, but not inhibited completely. PMID:16572793

  14. Toxicity of Nano-Zero Valent Iron to Freshwater and Marine Organisms

    PubMed Central

    Keller, Arturo A.; Garner, Kendra; Miller, Robert J.; Lenihan, Hunter S.

    2012-01-01

    We tested whether three commercial forms (uncoated, organic coating, and iron oxide coating) of nano zero-valent iron (nZVI) are toxic to freshwater and marine organisms, specifically three species of marine phytoplankton, one species of freshwater phytoplankton, and a freshwater zooplankton species (Daphnia magna), because these organisms may be exposed downstream of where nZVI is applied to remediate polluted soil. The aggregation and reactivity of the three types of nZVI varied considerably, which was reflected in their toxicity. Since levels of Fe2+ and Fe3+ increase as the nZVI react, we also evaluated their toxicity independently. All four phytoplankton species displayed decreasing population growth rates, and Daphnia magna showed increasing mortality, in response to increasing levels of nZVI, and to a lesser degree with increasing Fe2+ and Fe3+. All forms of nZVI aggregated in soil and water, especially in the presence of a high concentration of calcium ions in groundwater, thus reducing their transports through the environment. However, uncoated nZVI aggregated extremely rapidly, thus vastly reducing the probability of environmental transport and potential for toxicity. This information can be used to design a risk management strategy to arrest the transport of injected nZVI beyond the intended remediation area, by injecting inert calcium salts as a barrier to transport. PMID:22952836

  15. Advanced treatment of coking wastewater by coagulation and zero-valent iron processes.

    PubMed

    Lai, Peng; Zhao, Hua-zhang; Wang, Chao; Ni, Jin-ren

    2007-08-17

    Advanced treatment of coking wastewater was investigated experimentally with coagulation and zero-valent iron (ZVI) processes. Particular attention was paid to the effect of dosage and pH on the removal of chemical oxygen demand (COD) in the two processes. The results showed that ZVI was more effective than coagulation for advanced treatment of coking wastewater. The jar tests revealed that maximal COD removal efficiency of 27.5-31.8% could be achieved under the optimal condition of coagulation, i.e. 400mg/L of Fe(2)(SO(4))3 as coagulant at pH 3.0-5.0. On the other hand, the COD removal efficiency could be up to 43.6% under the idealized condition of ZVI upon 10 g/L active carbon and 30 g/L iron being dosed at pH 4.0. The mechanisms for COD removal in ZVI were dominated by coagulation, precipitation and oxidation-reduction. ZVI would also enhance the biodegradability of effluent by increasing BOD5/COD from 0.07 to 0.53. Moreover, some ester compounds could be produced in the reaction. Although ZVI was found more efficient than coagulation in eliminating low molecular weight (<2000 Da) compounds in the wastewater, there were still a few residual contaminants which could hardly be eliminated by either of the process. PMID:17267104

  16. [Performance Recoverability of Denitrifying Granular Sludge Under the Stressing Effect of Nanoscale Zero-valent Iron].

    PubMed

    Wang, Fan-fan; Qian, Fei-yue; Shen, Yao-liang; Wang, Jian-fang; Zhang, Yue-ru; Liu, Guo-xun

    2016-04-15

    To explore the potential stressing effect of nanoscale zero-valent iron (nZVI) on denitrifying granular sludge (DGS), the evolution of DGS denitrifying performance under different C/N ratios was investigated in this study, by carrying out batch tests of eight successive periods with the nZVI shock-loading. The results showed that the specific denitrification rate of µ value decreased when the nZVI dosage was higher than 5 mg · L⁻¹. Meanwhile, a positive correlation between the inhibition ratio (IR) of µ value and substrate C/N ratios or nZVI dosage was observed. When the nZVI dosage reached 100 mg · L⁻¹, both extracellular protein and polysaccharides concentrations decreased obviously. It would be beneficial to promote the recovery of DGS denitrifying activity and reduce the COD demanding to remove unit mass of nitrate, by increasing external carbon source with C/N ratios of higher than 4. On the basis of Freundlich and Langmuir adsorption isotherms, when higher C/N ratio was provided, stronger bioadsorption of nZVI would be achieved. During the recovery period, a significant improvement of DCS denitrifying performance under the high C/N ratio was expected, due to the continuous washout of total iron in sludge phase (Qe), while the µ value would reach or approach the one of the control group when Qe was lower than 0.4 mg · g⁻¹. PMID:27548972

  17. The use of zero-valent iron and biosand filtration to inactivate Escherichia coli O157:H7 in irrigation water

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Introduction: Foodborne pathogens can be disseminated to produce through contaminated irrigation water. Effective, low cost mitigation strategies, like biosand and zero-valent iron (ZVI) filtration, may be effective in decontaminating irrigation water. Purpose: To determine the effectiveness ...

  18. Standardization of the reducing power of zero-valent iron using iodine.

    PubMed

    Kim, Heonki; Yang, Haewon; Kim, Juyoung

    2014-01-01

    Because iron-based materials that are used for the permeable reactive barrier systems come in various shapes, sizes, and with various surface properties depending on the manufacturing sources, their reductive powers vary in a wide spectrum. A new experimental procedure to evaluate the reductive power of iron material was developed in this study. Tri-iodide (I3(-)) was used as the representative oxidizing agent that reacts with zero-valent iron (ZVI). Three iron-based materials (two scraps, two powders) and four chlorinated chemicals [perchloroethene (PCE), trichloroethene (TCE), 1,1,1-trichloroethane (TCA), and pentachlorophenol (PCP)] were used in this study. Redox reactions were conducted in glass vials containing aqueous solutions of chlorinated compounds or tri-iodide with known masses of iron material. After a predetermined reaction time each vial was opened and the solution was analyzed for the concentration of reduced compound. The apparent rate contant (k(i)(obs)) of iodine reduction reaction with ZVIs was found to be proportional to that (k(c)(obs)) of chlorinated contaminant. The surface area-normalized reduction rate constants (k(c)(nor)) for contaminants and tri-iodide (k(i)(nor)) were also proportional to each other. The ratio of rate constants, K(nor) (= k(c)(nor)/k(i)(nor)) was estimated for each contaminant; 3.29 × 10(-7), 5.86 × 10(-7), 6.70 × 10(-7), and 7.87 × 10(-10) M, for PCE, TCE, TCA, and PCP, respectively. The results of this study suggest that the reductive power of ZVI materials can be standardized using tri-iodide, and thus, can provide a good reference for the quantitative assessment of the reactivity of metallic reducing agents of environmental interest including ZVIs. PMID:24410682

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

    PubMed

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

    2012-01-01

    Sepiolite, a natural nano-material, was chosen as a carrier to prepare supported nanoscale zero-valent iron (nZVI). The effects of preparation conditions, including mass ratio of nZVI and activated sepiolite and preparation pH value, on properties of the supported nZVI were investigated. The results showed that the optimal mass ratio of nZVI and sepiolite was 1.12:1 and the optimal pH value was 7. The supported nZVI was characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and energy dispersive spectrometer (EDS), and furthermore an analogy model of the supported nZVI was set up. Compared with the nZVI itself, the supported nZVI was more stable in air and possessed better water dispersibility, which were beneficial for the degradation of bromamine acid aqueous solution. The degradation characteristics, such as effects of supported nZVI dosage, initial concentration and initial pH value of the solution on the decolorization efficiency were also investigated. The results showed that in an acidic environment the supported nZVI with a dosage of 2 g/L showed high activity in the degradation of bromamine acid with an initial concentration of 1,000 mg/L, and the degree of decolorization could reach up to 98%. PMID:23109568

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

    SciTech Connect

    Truex, Michael J.; Macbeth, Tamzen; Vermeul, Vincent R.; Fritz, Brad G.; Mendoza, Donaldo P.; Mackley, Rob D.; Wietsma, Thomas W.; Sandberg, Greg; Powell, Thomas; Powers, Jeff; Pitre, Emile; Michalsen, Mandy M.; Ballock-Dixon, Sage; Zhong, Lirong; Oostrom, Martinus

    2011-06-27

    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 volatilization 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.

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

    PubMed Central

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

    2014-01-01

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

  2. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron.

    PubMed

    Li, Huanxuan; Wan, Jinquan; Ma, Yongwen; Wang, Yan

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO4(-)) and hydroxyl radical (·OH) were found to be primary oxidants at pH3.0 and pH7.0, respectively while ·OH was the major specie to oxidize DBP at pH11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to OH, superoxide radical (O2(-)) was detected at pH11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH3.0 by GC-MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH3.0. PMID:27125682

  3. Reduction and immobilization of chromate in chromite ore processing residue with nanoscale zero-valent iron.

    PubMed

    Du, Jingjing; Lu, Jinsuo; Wu, Qiong; Jing, Chuanyong

    2012-05-15

    Chromite ore processing residue (COPR) poses a great environmental and health risk with persistent Cr(VI) leaching. To reduce Cr(VI) and subsequently immobilize in the solid matrix, COPR was incubated with nanoscale zero-valent iron (nZVI) and the Cr(VI) speciation and leachability were studied. Multiple complementary analysis methods including leaching tests, X-ray powder diffraction, X-ray absorption near edge structure (XANES) spectroscopy, and X-ray photoelectron spectroscopy (XPS) were employed to investigate the immobilization mechanism. Geochemical PHREEQC model calculation agreed well with our acid neutralizing capacity experimental results and confirmed that when pH was lowered from 11.7 to 7.0, leachate Cr(VI) concentrations were in the range 358-445mgL(-1) which contributed over 90% of dissolved Cr from COPR. Results of alkaline digestion, XANES, and XPS demonstrated that incubation COPR with nZVI under water content higher than 27% could result in a nearly complete Cr(VI) reduction in solids and less than 0.1mgL(-1) Cr(VI) in the TCLP leachate. The results indicated that remediation approaches using nZVI to reduce Cr(VI) in COPR should be successful with sufficient water content to facilitate electron transfer from nZVI to COPR. PMID:22417394

  4. Removal of hexavalent chromium from contaminated ground water using zero-valent iron nanoparticles.

    PubMed

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

    2012-06-01

    Batch experiments were conducted on ground water samples collected from a site contaminated with Cr(VI) to evaluate the redox potential of zero-valent iron (Fe(0)) nanoparticles for remediation of Cr(VI)-contaminated ground water. For this, various samples of contaminated ground water were allowed to react with various loadings of Fe(0) nanoparticles for a reaction period of 60 min. Data showed 100% reduction of Cr(VI) in all the contaminated ground water samples after treatment with 0.20 gL(-1) of Fe(0) nanoparticles. An increase in the reduction of Cr(VI) from 45% to 100% was noticed with the increase in the loading of Fe(0) nanoparticles from 0.05 to 0.20 gL(-1). Reaction kinetics of Cr(VI) reduction showed pseudo first-order kinetics with rate constant in the range of 1.1 × 10(-3) to 3.9 × 10(-3) min(-1). This work demonstrates the potential utility of Fe(0) nanoparticles in treatment and remediation of Cr(VI)-contaminated water source. PMID:21769560

  5. Characterization of green zero-valent iron nanoparticles produced with tree leaf extracts.

    PubMed

    Machado, S; Pacheco, J G; Nouws, H P A; Albergaria, J T; Delerue-Matos, C

    2015-11-15

    In the last decades nanotechnology has become increasingly important because it offers indisputable advantages to almost every area of expertise, including environmental remediation. In this area the synthesis of highly reactive nanomaterials (e.g. zero-valent iron nanoparticles, nZVI) is gaining the attention of the scientific community, service providers and other stakeholders. The synthesis of nZVI by the recently developed green bottom-up method is extremely promising. However, the lack of information about the characteristics of the synthetized particles hinders a wider and more extensive application. This work aims to evaluate the characteristics of nZVI synthesized through the green method using leaves from different trees. Considering the requirements of a product for environmental remediation the following characteristics were studied: size, shape, reactivity and agglomeration tendency. The mulberry and pomegranate leaf extracts produced the smallest nZVIs (5-10 nm), the peach, pear and vine leaf extracts produced the most reactive nZVIs while the ones produced with passion fruit, medlar and cherry extracts did not settle at high nZVI concentrations (931 and 266 ppm). Considering all tests, the nZVIs obtained from medlar and vine leaf extracts are the ones that could present better performances in the environmental remediation. The information gathered in this paper will be useful to choose the most appropriate leaf extracts and operational conditions for the application of the green nZVIs in environmental remediation. PMID:26151651

  6. Analytical characterisation of nanoscale zero-valent iron: A methodological review.

    PubMed

    Chekli, L; Bayatsarmadi, B; Sekine, R; Sarkar, B; Shen, A Maoz; Scheckel, K G; Skinner, W; Naidu, R; Shon, H K; Lombi, E; Donner, E

    2016-01-15

    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. PMID:26709296

  7. Filamentous sludge bulking control by nano zero-valent iron in activated sludge treatment systems.

    PubMed

    Xu, Shengnan; Sun, Minghao; Zhang, Chiqian; Surampalli, Rao; Hu, Zhiqiang

    2014-12-01

    Sludge bulking causes loss of biomass in the effluent and deterioration of effluent water quality. This study explored the use of nano zero-valent iron (NZVI with an average particle size of 55 ± 11 nm) for sludge bulking control. In two Modified Ludzack-Ettinger (MLE) activated sludge treatment systems, a single dose of NZVI at the final concentration of 100 mg Fe per L in the mixed liquor reduced the number of filamentous bacteria Type 021N by 2-3 log units (a reduction of 99.9 and 96.7% in MLE tank #1 and #2, respectively). The side effect of the use of NZVI depended on sludge bulking conditions and biomass concentration. In the system with sludge bulking and significant sludge loss (average biomass concentration of 1022 ± 159 COD mg per L or at the ratio of 0.098 g Fe per g biomass COD), the use of NZVI increased effluent COD, NH4(+)-N and NO2(-)-N concentrations, as also evident with the loss of nitrifying populations and nitrifying activities resulting in more than 40 days to have the full recovery of the activated sludge system. In contrast, in the system with the early stages of bulking and the biomass concentration of 1799 ± 113 COD mg per L (at the ratio of 0.056 g Fe per g biomass COD), the effluent water quality and overall bioreactor performance were only slightly affected for a few days. PMID:25386669

  8. Effective removal of nemacide fosthiazate from an aqueous solution using zero-valent iron.

    PubMed

    Wu, Junxue; Shen, Chongyang; Zhang, Hongyan; Lu, Weilan; Zhang, Yun; Wang, Chengju

    2015-09-15

    In this study, the removal of fosthiazate in an aqueous solution using zero valent iron (ZVI) and the related removal reaction mechanism were investigated. The results indicate that the dissipation of fosthiazate adheres to a pseudo-first order reaction law. The apparent rate constant of fosthiazate removal could be improved by increasing the ZVI dosage, control temperature and initial pH. The observed pseudo-first-order degradation rate constants (Kobs) of fosthiazate removal using ZVI were varied in the different electrolyte solutions, and were determined as follows: Kobs (MgSO4) < Kobs (KCl) < Kobs (Control)

  9. Remediation of trichloroethylene-contaminated groundwater by three modifier-coated microscale zero-valent iron.

    PubMed

    Han, Jun; Xin, Jia; Zheng, Xilai; Kolditz, Olaf; Shao, Haibing

    2016-07-01

    Building a microscale zero-valent iron (mZVI) reaction zone is a promising in situ remediation technology for restoring groundwater contaminated by trichloroethylene (TCE). In order to determine a suitable modifier that could not only overcome gravity sedimentation of mZVI but also improve its remediation efficiency for TCE, the three biopolymers xanthan gum (XG), guargum (GG), and carboxymethyl cellulose (CMC) were employed to coat mZVI for surface modification. The suspension stability of the modified mZVI and its TCE removal efficiency were systematically investigated. The result indicated that XG as a shear-thinning fluid showed the most remarkable efficiency of preventing mZVI from gravity sedimentation and enhancing the TCE removal efficiency by mZVI. In a 480-h experiment, the presence of XG (3 g L(-1)) increased the TCE removal efficiency by 31.85 %, whereas GG (3 g L(-1)) and CMC (3 g L(-1)) merely increased by 15.61 and 9.69 % respectively. The pH value, Eh value, and concentration of ferrous ion as functions of the reaction time were recorded in all the reaction systems, which indicated that XG worked best in buffering the pH value of the solution and inhibiting surface passivation of mZVI. PMID:27068901

  10. Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon

    USGS Publications Warehouse

    Lewis, Ariel S.; Huntington, Thomas G.; Marvin-DiPasquale, Mark C.; Amirbahman, Aria

    2016-01-01

    Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.

  11. [Simultaneous Biotransformation of Ammonium and Nitrate via Zero-Valent Iron on Anaerobic Conditions].

    PubMed

    Zhou, Jian; Huang, Yong; Yuan, Yi; Liu, Xin; Li, Xiang; Shen, Jie; Yang, Peng-bing

    2015-12-01

    Zero-valent iron (ZVI) was used to improve the biological autotrophic denitrification process between nitrate and ammonia by anaerobic ammonia oxidation ( ANAMMOX) bacteria. With the addition of ZVI, the biological autotrophic denitrification process could be reacted in the influent condition of pH was 7-8, at 35°C ±0.5°C, the concentration of ammonia was 50-100 mg · L⁻¹ and the concentration of nitrate was 50-100 mg · L⁻¹. The highest conversion rate could be reached to 17.2 mg · (L·h) ⁻¹. With the change of reaction time and the molar ratio of nitrate and ammonia in influent, the final molar conversion ratio of nitrate and ammonia in effluent fluctuated between 1.2-3. 5. The result showed that this autotrophic denitrification process was not belonged to elementary reaction. The mechanism of this autotrophic denitrification process could be summarized that with the reduction of ZVI, the nitrate could be reduced to nitrite. Hereafter, the ANAMMOX process reacted between the nitrite and ammonia. PMID:27011992

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

    PubMed

    Ma, Xingmao; Gurung, Arun; Deng, Yang

    2013-01-15

    Use of nano-scale zero valent iron (nZVI) for the treatment of various environmental pollutants has been proven successful. However, large scale introduction of engineered nanomaterials such as nZVI into the environment has recently attracted serious concerns. There is an urgent need to investigate the environmental fate and impact of nZVI due to the scope of its application. The goal of this study was to evaluate the toxicity and accumulation of bare nZVI by two commonly encountered plant species: cattail (Typha latifolia) and hybrid poplars (Populous deltoids×Populous nigra). Plant seedlings were grown hydroponically in a greenhouse and dosed with different concentrations of nZVI (0-1000 mg/L) for four weeks. The nZVI exhibited strong toxic effect on Typha at higher concentrations (>200 mg/L) but enhanced plant growth at lower concentrations. nZVI also significantly reduced the transpiration and growth of hybrid poplars at higher concentrations. Microscopic images indicated that large amount of nZVI coated on plant root surface as irregular aggregates and some nZVI penetrated into several layers of epidermal cells. Transmission electron microscope (TEM) and scanning transmission electron microscope (STEM) confirmed the internalization of nZVI by poplar root cells but similar internalization was not observed for Typha root cells. The upward transport to shoots was minimal for both plant species. PMID:23247287

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

    PubMed

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

    2015-01-01

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

  14. A field comparison of two reductive dechlorination (zero-valent iron and lactate) methods.

    PubMed

    Lacinova, Lenka; Kvapil, Petr; Cernik, Miroslav

    2012-01-01

    Two parallel pilot experiments were performed at Kurivody (Czech Republic) in order to compare two reductive remedial technologies for chlorinated ethenes - microbial dehalogenation assisted by lactate and chemical dehalogenation with zero-valent iron (nZVI) nanoparticles. The methods were applied at a site contaminated by tetrachlorethylene (PCE) and trichlorethylene (TCE), with total concentrations from 10 to 50 mg/l. Concentrations of chlorinated ethenes, inorganic components of interest, pH and oxidation reduction potential (ORP) were monitored at the site for a period up to 650 days. The method of biological reductive dechlorination supported by lactate showed a considerable removal of PCE and TCE, but temporary accumulation of transient reaction product 1,2-cis-dihloroethene. Reductive dechlorination with nZVI showed a significant reduction in the concentration of chlorinated ethenes without a formation of intermediate products. The development of pH showed only small changes due to the high buffering capacity of the aquifer. Both methods differ in the initial development of ORP, but over the long term showed similar values around 100 mV. Significant differences were observed for chemical oxygen demand, where groundwater after the application of nZVI showed no change in comparison to the application of lactate. The reductive effects of both agents were verified by changes in inorganic compound concentrations. PMID:22720397

  15. -encapsulated zero-valent iron nanoparticles for degradation of organic dyes

    NASA Astrophysics Data System (ADS)

    Mao, Zhou; Wu, Qingzhi; Wang, Min; Yang, Yushi; Long, Jia; Chen, Xiaohui

    2014-09-01

    A series of nanocomposites consisting of zero-valent iron nanoparticles (ZVI NPs) encapsulated in SiO2 microspheres were successfully synthesized through a successive two-step method, i.e., the wet chemical reduction by borohydride followed by a modified Stöber method. The as-synthesized nanocomposites were characterized using X-ray diffraction, field emission scanning electron microscopy, vibrating sample magnetometer, and inductively coupled plasma-atomic emission spectrometer. The catalytic performance of SiO2-encapsulated ZVI nanocomposites for the degradation of organic dyes was investigated using methylene blue (MB) as the model dye in the presence of H2O2. The results showed that the degradation efficiency and apparent rate constant of the degradation reaction were significantly enhanced with increased ZVI NPs encapsulated in SiO2 microspheres, whereas the dosage of H2O2 remarkably promoted degradation rate without affecting degradation efficiency. The content-dependent magnetic property ensured the excellent magnetic separation of degradation products under an external magnet. This strategy for the synthesis of SiO2-encapsulated ZVI NPs nanocomposites was low cost and easy to scale-up for industrial production, thereby enabling promising applications in environmental remediation.

  16. Modelling the remediation of contaminated groundwater using zero-valent iron barrier

    SciTech Connect

    Kwong, S.; Small, J.; Tahar, B.

    2007-07-01

    This paper presents results of modelling studies on remediation of groundwater contaminated with uranium using a zero-valent iron permeable reactive barrier (ZVI PRB) at the U.S. Oak Ridge Y-12 site that are used to establish modelling techniques that are of value to other sites such as in the UK. A systematic modelling methodology has been developed to study the problem by using a suite of modelling tools. Firstly a conceptual basis of the main chemical processes representing the remediation of uranium by the ZVI PRB is developed. Two main effects involving reduction and corrosion have been identified as being relevant for the remediation processes. These are then formulated and implemented using the reactive chemical model PHREEQC to provide underpinning chemical input parameters for subsequent reactive solute transport modelling using the TRAFFIC and PHAST codes. Initial results shows that modelling can be a very cost-effective means to study the hydrogeological and geochemical processes involved and to aid understanding of the remediation concept. The modelling approaches presented and lessons learnt are thought to be relevant to other cases of contaminated land study and are likely to be of value to site management concepts which consider on-site disposal of contaminated soils and materials. (authors)

  17. The use of zero-valent iron and ultrasonic energy for in-situ groundwater remediation

    SciTech Connect

    Afiouni, G.F.; Clausen, C.A.; Geiger, C.L.; Reinhart, D.; Ruiz, N.E.

    1996-12-31

    Contamination in groundwater in general and drinking water in particular has become a major concern in the twentieth century. EPA strictly regulates the amount of acceptable contamination to extremely low levels for chemical industries. Old techniques, such as pump-and-treat, has proven to have some limitation in dropping the concentrations to acceptable levels thus forcing research groups to look into other alternatives for groundwater remediation. A new technique is to implement an in situ treatment of groundwater depending mainly on the natural water flow through a treatment wall. This active wall would consist of zero-valent-iron, with high surface area to mass ratio, in order to accelerate the kinetics of the dehalogenation of chlorinated organic molecules, mainly trichloroethylene TCE, into environmentally acceptable hydrocarbons that can be consumed by microorganisms underground. In addition, ultrasonic chemistry is co-applied in order to replenish the oxidized metal surface area i.e. to help in maintaining wall activity which theoretically should increase the wall lifetime. Data from both batch and column reactions show the feasibility of such a procedure. Kinetic data will be presented.

  18. Ageing decreases the phytotoxicity of zero-valent iron nanoparticles in soil cultivated with Oryza sativa.

    PubMed

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

    2016-08-01

    This paper was aimed to study the impact of "ageing" (aged in non-saturated soil for 2 and 4 weeks prior to exposure) nanoscale zero-valent iron (nZVI) on the terrestrial plant. The effects of nZVI on Oryza Sativa germination, seedlings growth, chlorophyll biosynthesis, oxidative stress and the activities of antioxidant enzymes at low (250 mg/kg) and high (1000 mg/kg) concentrations were investigated in this study. The results showed that neither the freshly added nor the "ageing" nZVI to the soil had a significant effect on germination, regardless of concentration. At the low concentration, the freshly added nZVI had no visible toxic effects on the rice seedlings growth, but the rice seedlings exhibited obvious toxic symptoms at the high concentration. At the high concentration, toxicity effects of nZVI were reduced after aging with 2 and 4 weeks in soils compared to fresh nZVI, but the "ageing" nZVI continued to significantly inhibit the rice seedlings growth compared with the control, and the inhibition rates of 2 and 4-week-old nZVI were not significantly different. The mechanism of ageing decreased the phytotoxicity of nZVI was due to nZVI particles incomplete oxidation, and some of which had remained in the soil after 4 weeks aged. PMID:27207497

  19. Degradation of carbon tetrachloride in the presence of zero-valent iron.

    SciTech Connect

    Alvarado, J. S.; Rose, C.; LaFreniere, L.; Environmental Science Division

    2010-01-01

    Efforts to achieve the decomposition of carbon tetrachloride through anaerobic and aerobic bioremediation and chemical transformation have met with limited success because of the conditions required and the formation of hazardous intermediates. Recently, particles of zero-valent iron (ZVI) have been used with limited success for in situ remediation of carbon tetrachloride. We studied a modified microparticulate product that combines controlled-release carbon with ZVI for stimulation of in situ chemical reduction of persistent organic compounds in groundwater. With this product, a number of physical, chemical, and microbiological processes were combined to create very strongly reducing conditions that stimulate rapid, complete dechlorination of organic solvents. In principle, the organic component of ZVI microparticles is nutrient rich and hydrophilic and has high surface area capable of supporting the growth of bacteria in the groundwater environment. In our experiments, we found that as the bacteria grew, oxygen was consumed, and the redox potential decreased to values reaching -600 mV. The small modified ZVI particles provide substantial reactive surface area that, in these conditions, directly stimulates chemical dechlorination and cleanup of the contaminated area without accumulation of undesirable breakdown products. The objective of this work was to evaluate the effectiveness of ZVI microparticles in reducing carbon tetrachloride under laboratory and field conditions. Changes in concentrations and in chemical and physical parameters were monitored to determine the role of the organic products in the reductive dechlorination reaction. Laboratory and field studies are presented.

  20. Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon.

    PubMed

    Lewis, Ariel S; Huntington, Thomas G; Marvin-DiPasquale, Mark C; Amirbahman, Aria

    2016-05-01

    Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails (Lymnaea stagnalis) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment. PMID:26874318

  1. Reductive Removal of Selenate in Water Using Stabilized Zero-Valent Iron Nanoparticles.

    PubMed

    Liu, Hongfang; Cai, Zhengqing; Zhao, Xiao; Zhao, Dongye; Qian, Tianwei; Bozack, Michael; Zhang, Mingang

    2016-08-01

    Polysaccharide-stabilized zero-valent iron (ZVI) nanoparticles were synthesized using sodium carboxymethyl cellulose (CMC) or starch as stabilizer, and tested for reductive removal of selenate in water. Batch kinetic tests showed that the stabilized ZVI nanoparticles offer much faster selenate removal than bare ZVI particles at both pH 6.0 and pH 8.4. X-ray photoelectron spectroscopy (XPS) analyses confirmed Se(VI) was transformed to Se(IV) and Se(0), which are removed along with the nanoparticles. Neutral pH (~7) was found to be most favorable for the reductive removal. Decreasing pH to 5.0 or increasing it to 8.0 reduced the removal rate of CMC-stabilized ZVI by a factor of 4.6 or 1.3, respectively, based on the observed first-order-rate constant. Dissolved organic matter (DOM) at 5 mg/L as total organic carbon (TOC) had modest inhibitive effect, but DOM at 25 mg/L TOC decreased selenate removal by 25%. The stabilized nanoparticles hold the potential to facilitate in situ remediation of selenate-contaminated soil and groundwater. PMID:27456140

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  3. Removal Rates of Aqueous Cr(VI) by Zero-Valent Iron Measured Under Flow Conditions

    SciTech Connect

    Kaplan, D.I.

    2002-05-10

    Studies were undertaken to measure the rate of Cr(VI) removal from the aqueous phase by zero-valent iron, Fe(0), under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a groundwater remediation technology that replaces the sand in a filter pack of a conventional well with a reactive material, such as Fe(0). The pseudo-first-order rate coefficients measured under flow conditions were comparable to those previously measured under batch conditions that had significantly greater ratios of solution volume to Fe(0) surface area. Between the range of 20 and 100 weight percent Fe(0), there was little measurable change in the reaction kinetics. Thus, it may be possible to include sand into the reactive filter packs in the event it is necessary to increase filter pack porosity or to decrease the accumulation of secondary reaction products that may lead to filter pack plugging. Background water chemistry had only marginal effects on reaction rate coefficients. The reaction rates measured in this study indicated that an Fe(0) filter pack could be used to lower Cr(VI) concentrations by several orders of magnitude in a once-through mode of operation of the Reactive Well Technology.

  4. Modelling of sequential groundwater treatment with zero valent iron and granular activated carbon.

    PubMed

    Bayer, Peter; Finkel, Michael

    2005-06-01

    Multiple contaminant mixtures in groundwater may not efficiently be treated by a single technology if contaminants possess rather different properties with respect to sorptivity, solubility, and degradation potential. An obvious choice is to use sequenced units of the generally accepted treatment materials zero valent iron (ZVI) and granular activated carbon (GAC). However, as the results of this modelling study suggest, the required dimensions of both reactor units may strongly differ from those expected on the grounds of a contaminant-specific design. This is revealed by performing an analysis for a broad spectrum of design alternatives through numerical experiments for selected patterns of contaminant mixtures consisting of monochlorobenzene, tetrachloroethylene, trichloroethylene (TCE), cis-1,2-dichloroethylene (cis-DCE), and vinyl chloride (VC). It is shown that efficient treatment can be achieved only if competitive sorption effects in the GAC unit as well as the formation of intermediate products in the ZVI unit are carefully taken into account. Cost-optimal designs turned out to vary extremely depending on the prevailing conditions concerning contaminant concentrations, branching ratios, and unit costs of both reactor materials. Where VC is the critical contaminant, due to high initial concentration or extensive production as an intermediate, two options are cost-effective: an oversized ZVI unit with an oversized GAC unit or a pure GAC reactor. PMID:15949610

  5. Zero-valent iron-activated persulfate oxidation of a commercial alkyl phenol polyethoxylate.

    PubMed

    Temiz, Kubra; Olmez-Hanci, Tugba; Arslan-Alaton, Idil

    2016-07-01

    Aqueous Triton X-45 (TX-45; 20 mg/L; original total organic carbon (TOC) = 14 mg/L), a representative, commercially important alkylphenol polyethoxylate, was subjected to persulfate (PS) oxidation activated with zero-valent iron (ZVI) nanoparticles. After optimization of the ZVI/PS treatment combination (1 g/L ZVI; 2.5 mM PS at pH5) in terms of pH (3-9), ZVI (0.5-5 g/L) and PS (0.5-5.0 mM) concentrations, TX-45 could be efficiently (>90%) degraded within short treatment periods (<60 min) accompanied with significant (>40%) TOC removals. The degree of PS consumption and Fe release was also followed during the experiments and a positive correlation existed between enhanced TX-45 removals and ZVI-activated PS consumption rates accompanied with a parallel Fe release. Acute toxicity tests were conducted using two different bioassays to examine the toxicological safety of the ZVI/PS oxidation system. Acute toxicity profiles significantly decreased from an original value of 66% relative inhibition to 21% and from 16% relative inhibition to non-toxic values according to Vibrio fischeri and Pseudokirchneriella subcapitata bioassays, respectively. The photobacterium V. fischeri appeared to be more sensitive to TX-45 and its degradation products than the microalgae P. subcapitata. PMID:26797469

  6. Study on treatment of coking wastewater by biofilm reactors combined with zero-valent iron process.

    PubMed

    Lai, Peng; Zhao, Hua-Zhang; Zeng, Ming; Ni, Jin-Ren

    2009-03-15

    Experiments were conducted to investigate the behavior of the integrated system with biofilm reactors and zero-valent iron (ZVI) process for coking wastewater treatment. Particular attention was paid to the performance of the integrated system for removal of organic and inorganic nitrogen compounds. Maximal removal efficiencies of chemical oxygen demand (COD), ammonia nitrogen (NH(3)-N) and total inorganic nitrogen (TIN) were up to 96.1, 99.2 and 92.3%, respectively. Moreover, it was found that some phenolic compounds were effectively removed. The refractory organic compounds were primarily removed in ZVI process of the integrated system. These compounds, with molecular weights either ranged 10,000-30,000 Da or 0-2000 Da, were mainly the humic acid (HA) and hydrophilic (HyI) compounds. Oxidation-reduction and coagulation were the main removal mechanisms in ZVI process, which could enhance the biodegradability of the system effluent. Furthermore, the integrated system showed a rapid recovery performance against the sudden loading shock and remained high efficiencies for pollutants removal. Overall, the integrated system was proved feasible for coking wastewater treatment in practical applications. PMID:18639983

  7. Impact of nanoscale zero valent iron on bacteria is growth phase dependent.

    PubMed

    Chaithawiwat, Krittanut; Vangnai, Alisa; McEvoy, John M; Pruess, Birgit; Krajangpan, Sita; Khan, Eakalak

    2016-02-01

    The toxic effect of nanoscale zero valent iron (nZVI) particles on bacteria from different growth phases was studied. Four bacterial strains namely Escherichia coli strains JM109 and BW25113, and Pseudomonas putida strains KT2440 and F1 were experimented. The growth curves of these strains were determined. Bacterial cells were harvested based on the predetermined time points, and exposed to nZVI. Cell viability was determined by the plate count method. Bacterial cells in lag and stationary phases showed higher resistance to nZVI for all four bacterial strains, whereas cells in exponential and decline phases were less resistant to nZVI and were rapidly inactivated when exposed to nZVI. Bacterial inactivation increased with the concentration of nZVI. Furthermore, less than 14% bacterial inactivation was observed when bacterial cells were exposed to the filtrate of nZVI suspension suggesting that the physical interaction between nZVI and cell is necessary for bacterial inactivation. PMID:26378872

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

    PubMed Central

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

    2015-01-01

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

  9. Reductive degradation of carbaryl in water by zero-valent iron.

    PubMed

    Ghauch, A; Gallet, C; Charef, A; Rima, J; Martin-Bouyer, M

    2001-02-01

    Reduction of carbaryl solution by zero-valent iron powder (ZVIP) was studied in a rotator batch system (70 rpm) in order to evaluate the utility of this reaction in remediation of carbamate contaminated water. Degradation with different amount of ZVIP: 0.01, 0.02, 0.03, 0.04 g/ml at pH 6.6 and at ambient temperature was investigated. The results show that the process exhibits a degradation rate appearing to be directly proportional to the surface contact area of ZVIP (325-mesh) with the carbaryl molecules. Three analytical techniques were used to monitor carbaryl degradation: (1) A UV-Vis diode array spectrophotometer was used to record all spectra. (2) A high performance liquid chromatography was used to separate by-products and examine the evolution of breakdown products. (3) A home-built spectrophosphorimeter that uses the solid surface room temperature phosphorescence (SSRTP) was employed to observe selectively the decline of the carbaryl concentration at different amount of ZVIP on Whatman no. 1 filter paper. Results show that the reducing degradation of carbaryl with ZVIP as the source of electrons is effective with a half-life close to several minutes. PMID:11100794

  10. Enhanced transport of Si-coated nanoscale zero-valent iron particles in porous media.

    PubMed

    HonetschlÄgerová, Lenka; Janouškovcová, Petra; Kubal, Martin

    2016-01-01

    Laboratory column experiments were conducted to evaluate the effect of previously described silica coating method on the transport of nanoscale zero-valent iron (nZVI) in porous media. The silica coating method showed the potential to prevent the agglomeration of nZVI. Transport experiments were conducted using laboratory-scale sand-packed columns at conditions that were very similar of natural groundwater. Transport properties of non-coated and silica-coated nZVI are investigated in columns of 40 cm length, which were filled with porous media. A suspension was injected in three different Fe particle concentrations (100, 500, and 1000 mg/L) at flow 5  mL/min. Experimental results were compared using nanoparticle attachment efficiency and travel distances which were calculated by classical particle filtration theory. It was found that non-coated particles were essentially immobile in porous media. In contrast, silica-coated particles showed significant transport distances at the tested conditions. Results of this study suggest that silica can increase nZVI mobility in the subsurface. PMID:26582314

  11. Kinetics of Nutrient Removal by Nano Zero-Valent Iron under Different Biochemical Environments.

    PubMed

    Xu, Shengnan; Hu, Zhiqiang

    2015-06-01

    The effectiveness of nano zero-valent iron (NZVI; an average size of 55 nm at a concentration of 200 mg Fe/L) in nutrient removal was determined under anaerobic, anoxic, and aerobic conditions. Compared to the rate of reduction of nitrate nitrogen (NO3--N) to ammoniacal nitrogen (NH4+-N) by NZVI alone, the presence of activated sludge increased the rate of complete reduction by 300%. About 31% of NO3--N was converted to NH4+-N through NZVI-facilitated dissimilatory nitrate reduction to ammonium, while 56% of NO3--N was removed by heterotrophic denitrification. The presence of sludge reduced the rates of phosphorus removal by NZVI, with the first-order reaction rate constants of 0.06/hour, 0.42/hour, and 0.18/hour under anaerobic, anoxic, and aerobic conditions, respectively. The highest phosphorus removal efficiency (95%) by NZVI was observed under anoxic abiotic conditions, whereas the efficiency dropped to 31% under anaerobic biotic conditions, which was attributed to significant sludge-facilitated NZVI agglomeration. PMID:26459816

  12. Ultrasound-assisted synthesis of nanosized zero-valent iron for metal cations extraction and wastewater treatment applications

    NASA Astrophysics Data System (ADS)

    Mikhailov, I. Yu; Lysov, D. V.; Levina, V. V.; Mazov, I. N.; Gusev, A. A.; Yudintseva, T. I.; Kuznetsov, D. V.

    2016-01-01

    Nanosized zero-valent iron has shown good results in wastewater treatment and activation of physicochemical processes. Its applications in modern industry are complicated by high production costs of nanomaterials produced via existing synthesis routes. Therefore there is a need of cheap and high-productive methods of nanosized zero-valent iron with advanced functional properties. Improvement of oxidative conditions with additions may find its place in extraction of rare-earth metals, where high cost of nanomaterials could be viable. In this paper we studied an effect of ultrasonic irradiation on specific surface area and particle size of nanosized zero-valent iron synthesized by methods of chemical precipitation with high- temperature reduction in hydrogen flow and sodium borohydride reduction. Obtained results showed significant decrease of particle size and differences in particles morphology depending on presence of ultrasonication during synthesis and on chosen method. For ultrasonic-assisted synthesis with 100% amplitude, particle size calculated from specific surface area was 70 nm for sample synthesized by chemical precipitation with high-temperature reduction and 35 nm for borohydide reduction method compared to 63 nm for reference sample without ultrasonication.

  13. Detoxification of PAX-21 ammunitions wastewater by zero-valent iron for microbial reduction of perchlorate.

    PubMed

    Ahn, Se Chang; Cha, Daniel K; Kim, Byung J; Oh, Seok-Young

    2011-08-30

    US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO(4)(-)) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21 wastewater was rapidly decreased to an undetectable level in 2 days. This result demonstrated that iron treatment not only removed energetic compounds but also eliminated the toxic constituents that inhibited the subsequent microbial process. PMID:21700387

  14. Effects of pH on dechlorination of trichloroethylene by zero-valent iron.

    PubMed

    Chen, J L; Al-Abed, S R; Ryan, J A; Li, Z

    2001-05-30

    The surface normalized reaction rate constants (k(sa)) of trichloroethylene (TCE) and zero-valent iron (ZVI) were quantified in batch reactors at pH values between 1.7 and 10. The k(sa) of TCE linearly decreased from 0.044 to 0.009l/hm(2) between pH 3.8 and 8.0, whereas the k(sa) at pH 1.7 was more than an order higher than that at pH 3.8. The degradation of TCE was not observed at pH values of 9 and 10. The k(sa) of iron corrosion linearly decreased from 0.092 to 0.018l/hm(2) between pH 4.9 and 9.8, whereas it is significantly higher at pH 1.7 and 3.8. The k(sa) of TCE was 30-300 times higher than those reported in literature. The difference can be attributed to the pH effects and precipitation of iron hydroxide. The k(sa) of TCE degradation and iron corrosion at a head space of 6 and 10ml were about twice of those at zero head space. The effect was attributed to the formation of hydrogen bubbles on ZVI, which hindered the transport the TCE between the solution and reaction sites on ZVI. The optimal TCE degradation rate was achieved at a pH of 4.9. This suggests that lowering solution pH might not expedite the degradation rate of TCE by ZVI as it also caused faster disappearance of ZVI, and hence decreased the ZVI surface concentration. PMID:11348735

  15. Oxygen controlled product formation in CCl{sub 4} dechlorination using zero-valent iron

    SciTech Connect

    Helland, B.R.; Alvarez, P.J.J.; Schnoor, J.L.

    1995-12-01

    Carbon tetrachloride (CCl{sub 4}) was abiotically dechlorinated using zero-valent iron powder (Fe{sup o}) to yield chloroform (CHCl{sub 3}) and methylene chloride (CH{sub 2}Cl{sub 2}), which did not undergo further dechlorination. Dechlorination was rapid and approximated first-order kinetics in the range of concentrations tested (CCl{sub 4}: 1.5 to 5.5 {mu}M; Fe{sup o}: 1 to 10 g per 265 mL distilled deionized water). Initial dechlorination rate coefficients for anoxic batch reactors (0.290 {plus_minus} 0.009 hr{sup -1} for 1 g Fe{sup o}; 1.723 {plus_minus} 0.078 hr{sup -1} for 10 g Fe{sup o}) increased with iron surface area (initially 2.4 {plus_minus} 0.2 m{sup 2}/g). Dechlorination also occurred under oxic conditions, although rates were significantly slower (e.g., 0.085 {plus_minus} 0.041 hr{sup -1} for 1 g Fe{sup o} and 7.4 mg/L initial dissolved oxygen). Rate coefficients increased with time, probably due to an increase in reactive surface area from pitting and dissolution of the iron surface. A rapid pH increase was synchronous to dissolved oxygen consumption, and the pH remained constant after oxygen depletion. This was attributed to the proton and oxygen consuming aerobic corrosion of the Fe{sup o} surface. Recalcitrant CH{sub 2}Cl{sub 2} was decreased in the presence of dissolved oxygen, which reacted with dechlorinated intermediates to yield less environmentally onerous products such as formic acid and carbon monoxide.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  17. Performance enhancement of zero valent iron based systems using depassivators: Optimization and kinetic mechanisms.

    PubMed

    Ansaf, Karim Vayalunkal Karottu; Ambika, Selvaraj; Nambi, Indumathi Manivannan

    2016-10-01

    The long-term ability of Zero-Valent Iron (ZVI) in contaminant removal relies on the effectiveness of iron to serve as electron donor, which makes it a versatile remediation material. However, the formation of oxide and hydroxide layers results in passive layer on ZVI surface during contaminant removal hinders its reactivity. The focus of this research was to evaluate the performance of corrosive agents such as acetic acid (HAc), aluminium sulphate (Alum) and potassium chloride (KCl) as depassivators to overcome passivation for sustainability and longevity. Batch experiments using seven combinations of the above chemicals were conducted to optimize the dosage of depassivators based on passive layer removal. The influence of depassivators in catalytic activity of ZVI in removing Cr(6+) was evaluated. The passive layer on ZVI particles was characterized using Scanning Electron Microscopy (SEM) and confirmed by Energy-Dispersive X-ray spectroscopy (EDAX) analysis. The major mechanisms in passive layer removal was found to be H(+) ion embrittlement followed by uniform depassivation when [HAc] was used and pitting corrosion when [Alum] and [KCl]were used. All the seven sets of chemicals enabled depassivation, but considering the criteria of maximum depassivation, catalytic activity and long term reactivity the depassivation treatments were effective in order as [HAc-Alum] > [HAc-Alum-KCl] >[HAc] > [Alum] > [HAc-KCl] > [KCl] > [Alum-KCl]. The kinetic rate of ZVI using [HAc-Alum] and [Alum] was relatively unchanged over the pH range of 4-10, made it suitable for ex-situ remediation. This insignificant influence of initial pH in catalytic activity of ZVI along with the improvement in longevity and sustainability makes it suitable for effective water treatment applications. The present work has successfully demonstrated that chemical depassivation can restore considerable reactivity of ZVI in the existing permeable reactive barriers. PMID:27395028

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

    PubMed

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

    2016-05-15

    Nanoscale zero-valent iron (NZVI) is increasingly used for reducing chlorinated organic contaminants in soil or groundwater. However, little is known about what impact the particles will have on the biochemical processes and the indigenous microbial communities. Nanoiron reactivity is affected by the structure and morphology of nanoparticles that complicates the applicability in bioremediation. In this study, the effect of precursors (ferrous sulfate and ferric chloride) and reducing agents (sodium dithionite and sodium borohydride) on the morphology and the reactivity of NZVIs was investigated. We also studied the impact of differently synthesized NZVIs on microbial community, which take part in reductive dechlorination. We demonstrated that both the applied iron precursor and the reducing agent had influence on the structure of the nanoparticles. Spherical nanoparticles with higher Fe(0) content (>90%) was observed by using sodium borohydride as reducing agent, while application of sodium dithionite as reducing agent resulted nanostructures with lower Fe(0) content (between 68,7 and 85,5%). To determine the influence of differently synthesized NZVIs on cell viability anaerobic enriched microcosm were used. NVZI was used in 0.1 g/L concentration in all batch experiments. Relative amount of Dehalococcoides, sulfate reducers (SRBs) and methanogens were measured by quantitative PCR. We found that the relative amount of Dehalococcoides slowly decreased in all experiments independently from the precursor and reducing agent, whereas the total amount of microbes increased. The only clear distinction was in relative amount of sulfate reducers which were higher in the presence of NZVIs synthesized from sodium dithionite. PMID:26994337

  19. Influence of zero-valent iron nanoparticles on nitrate removal by Paracoccus sp.

    PubMed

    Liu, Yan; Li, Shibin; Chen, Zuliang; Megharaj, Mallavarapu; Naidu, Ravi

    2014-08-01

    Nitrate contamination in drinking water is a major threat to public health. This study investigated the efficiency of denitrification of aqueous solutions in the co-presence of synthesized nanoscale zero-valent iron (nZVI; diameter: 20-80 nm) and a previously isolated Paracoccus sp. strain YF1. Various influencing factors were studied, such as oxygen, pH, temperature, and anaerobic corrosion products (Fe(2+), Fe(3+) and Fe3O4). With slight toxicity to the strain, nZVI promoted denitrification efficiency by providing additional electron sources under aerobic conditions. For example, 50 mg L(-1) nZVI increased the nitrate removal efficiency from 66.9% to 85.2%. However, a high concentration of nZVI could lead to increased production of Fe(2+), a toxic ion which could compromise the removal efficiency. Kinetic studies suggest that denitrification by both free cells, and nZVI-amended cells fitted well to the zero-order model. Temperature and pH are the major factors affecting nitrate removal and cell growth, with or without the presence of nZVI. In this study, nitrate removal and cell growth increased in the pH range of 6.5-8.0, and temperature range of 25-35 °C. These conditions favor the growth of the strain, which dominated denitrification in all scenarios involved. As for anaerobic corrosion products, compared with Fe(2+) and Fe(3+), Fe3O4 promoted denitrification by serving as an electron donor. Finally, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirmed attachments of nZVI on the surface of the cell, and the formation of iron oxides. This study indicated that, as an electron donor source with minimal cellular toxicity, nZVI could be used to promote denitrification efficiency under biotic conditions. PMID:24630453

  20. Reductive precipitation of uranium(VI) by zero-valent iron

    SciTech Connect

    Gu, B.; Dickey, M.J.; Yin, X.; Dai, S.; Liang, L.

    1998-11-01

    This study was undertaken to determine the effectiveness of zero-valent iron (Fe{sup 0}) and several adsorbent materials in removing uranium (U) from contaminated groundwater and to investigate the rates and mechanisms that are involved in the reactions. Fe{sup 0} filings were used as reductants, and the adsorbents included peat materials, iron oxides, and a carbon-based sorbent (Cercona Bone-Char). Results indicate that Fe{sup 0} filings are much more effective than the adsorbents in removing uranyl (UO{sub 2}{sup 2+}) from the aqueous solution. Nearly 100% of U was removed through reactions with Fe{sup 0} at an initial concentration up to 76 mM. Results from the batch adsorption and desorption and from spectroscopic studies indicate that reductive precipitation of U on Fe{sup 0} is the major reaction pathway. Only a small percentage of UO{sub 2}{sup 2+} appeared to be adsorbed on the corrosion products of Fe{sup 0} and could be desorbed by leaching with a carbonate solution. The study also showed that the reduced U(IV) species on Fe{sup 0} surfaces could be reoxidized and potentially remobilized when the reduced system becomes more oxidized. Results of this research support the application of the permeable reactive barrier technology using Fe{sup 0} as a reactive media to intercept U and other groundwater contaminants migrating to the tributaries of Bear Creek at the US Department of Energy`s Y-12 Plant located in Oak Ridge, TN.

  1. Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

    SciTech Connect

    Phillips, Debra Helen; Gu, Baohua; Watson, David B; Roh, Yul

    2003-03-01

    Permeable reactive barriers (PRBs) of zero-valent iron (Fe{sup 0}) are increasingly being used to remediate contaminated ground water. Corrosion of Fe{sup 0} filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe{sup 0} PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe{sup 0} reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe{sup 0} PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105 C. We conclude that care must be taken during sample preparation of Fe{sup 0} PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

  2. Biogeochemical dynamics in zero-valent iron columns: Implications for permeable reactive barriers

    SciTech Connect

    Gu, B.; Phelps, T.J.; Liang, L.; Palumbo, A.V.; Jacobs, G.K.; Dickey, M.J.; Roh, Y.; Kinsall, B.L.

    1999-07-01

    The impact of microbiological and geochemical processes has been a major concern for the long-term performance of permeable reactive barriers containing zero-valent iron (Fe{sup 0}). To evaluate potential biogeochemical impacts, laboratory studies were performed over a 5-month period using columns containing a diverse microbial community. The conditions chosen for these experiments were designed to simulate high concentrations of bicarbonate and sulfate containing groundwater regimes. Groundwater chemistry was found to significantly affect corrosion rates of Fe{sup 0} filings and resulted in the formation of a suite of mineral precipitates. HCO{sub 3}{sup {minus}} ions in SO{sub 4}{sup 2{minus}}-containing water were particularly corrosive to Fe{sup 0}, resulting in the formation of ferrous carbonate and enhanced H{sub 2} gas generation that stimulated the growth of microbial populations and increased SO{sub 4}{sup 2{minus}} reduction. Major mineral precipitates identified included lepidocrocite, akaganeite, mackinawite, magnetite/maghemite, goethite, siderite, and amorphous ferrous sulfide. Sulfide was formed as a result of microbial reduction of SO{sub 4}{sup 2{minus}} that became significant after about 2 months of column operations. This study demonstrates that biogeochemical influences on the performance and reaction of Fe{sup 0} may be minimal in the short term, necessitating longer-term operations to observe the effects of biogeochemical reactions on the performance of Fe{sup 0} barriers. Although major failures of in-ground treatment barriers have not been problematic to date, the accumulation of iron oxyhydroxides, carbonates, and sulfides from biogeochemical processes could reduce the reactivity and permeability of Fe{sup 0} beds, thereby decreasing treatment efficiency.

  3. Zero-valent Iron Emplacement in Permeable Porous Media Using Polymer Additions

    SciTech Connect

    Oostrom, Mart; Wietsma, Thomas W.; Covert, Matthew A.; Vermeul, Vince R.

    2007-02-15

    At the Hanford Site in Washington, an extensive In Situ Redox Manipulation (ISRM) permeable reactive barrier was installed to prevent chromate from reaching the Columbia River. However, chromium has been detected in several wells, indicating a premature loss of the reductive capacity in the aquifer. One possible cause for premature chromate breakthrough is associated with the presence of high-permeability zones in the aquifer. The potential emplacement of zero-valent iron (Fe0) into high-permeability Hanford sediments to enhance the barrier’s reductive capacity using shear-thinning fluids containing polymers was investigated in three-dimensional wedge-shaped aquifer models. Porous media were packed in the wedge-shaped flow cell to create either a heterogeneous layered system with a high-permeability zone between two low-permeability zones or a high-permeability channel surrounded by low-permeability materials. The injection flow rate, polymer type, polymer concentration, and injected pore volumes were determined based on preliminary short- and long-column experiments. The flow cell experiments indicated that iron concentration enhancements of at least 0.6% (w/w) could be obtained using moderate flow rates and injection of 30 pore volumes. The aqueous pressure increased by a maximum of 25 KPa during infiltration, but a decrease in permeability was not observed. Under optimal conditions, the 0.6% amended Fe0 concentration would provide approximately 20 times the average reductive capacity that is provided by the dithionite-reduced Fe (II) in the ISRM barrier.

  4. Arsenate removal from water by zero-valent iron/activated carbon galvanic couples.

    PubMed

    Dou, Xiaomin; Li, Rui; Zhao, Bei; Liang, Wenyan

    2010-10-15

    Galvanic couples composed of zero-valent iron and activated carbon (Fe(0)/AC) were investigated for As(V) removal from water. The effects of Fe(0) to AC mass ratio (FCR), solution pH, ionic strength and co-existing anions (phosphate, carbonate, silicate, nitrate, chloride and sulfate) and humic acid (HA) on As(V) removal were evaluated. The results showed that the optimum mass ratio was 1:1, and Fe(0)/AC with this ratio was more effective for As(V) removal than Fe(0) and AC alone at pH of 7 and ion strength of 0.03 M NaCl. The enhanced performance for As(V) removal was fulfilled through an accelerated corrosion process of Fe(0), which meant more corrosion products for efficient As(V) removal. The As(V) removal followed a pseudo-first order reaction. The rate constants (k) for 1:1 Fe(0)/AC and Fe(0) alone were 0.802 and 0.330 h(-1), respectively. Potentiodynamic polarization scans further confirmed that Fe(0) corrosion was promoted when Fe(0) was coupled with AC. Except silicates, other co-existing anions promoted As(V) removal. No reduction form of As (As(III) or As(0)) could be detected on iron corrosion products (ICPs) and in solutions. Identified ICPs included poorly crystallized lepidocrocite (gamma-FeOOH) and magnetite/maghemite (Fe(3)O(4)/gamma-Fe(2)O(3)) for both of Fe(0)/AC and Fe(0) systems. In conclusion, the Fe(0)/AC couple exhibited higher As removal performance than that of Fe(0) alone from water. PMID:20599323

  5. Mechanism of Co(II) adsorption by zero valent iron/graphene nanocomposite.

    PubMed

    Xing, Min; Xu, Lejin; Wang, Jianlong

    2016-01-15

    Nanoscale zero valent iron (ZVI)/graphene (GF) composite was prepared and characterized by Brunauer-Emmett-Teller (BET) surface area measurement and zeta potential determination. The adsorption isotherm of Co(II) in aqueous solution, as well as the influence of pH values and ionic strengths was studied. The mechanism of Co(II) adsorption by GF was investigated through analyzing the sorption products at initial pH of 3.0, 6.0 and 9.0 using high-resolution transmission electron microscope with energy dispersive X-ray detector (HRTEM-EDX), X-ray diffraction (XRD), vibrating-sample magnetometer (VSM), Raman spectra, X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) measurement. The results indicated that Langmuir isotherm model fitted well and the adsorption capacity was 131.58 mg g(-1) at 30°C. Adsorption capacity was not significantly influenced by ionic strength and kept high at pH 4.0∼9.0. The detail information of GF-Co interaction at different initial pH values was obtained using XAFS analysis combined with other characterization methods. Coordination numbers (CN) and interatomic distances (R) of both Fe and Co were given. At pH 3.0 and pH 6.0, the Co-substituted iron oxides transformed to CoFe2O4-like structure, while at pH 9.0 they changed to green rust-like phases. Co occupied preferentially in the octahedral sites in acid solution. The adsorption mechanism of Co(II) was attributed to inner-sphere complexation and dissolution/re-precipitation of the substituted metal oxides. PMID:26368802

  6. Assessing the capacity of zero valent iron nanofluids to remediate NAPL-polluted porous media.

    PubMed

    Tsakiroglou, Christos; Terzi, Katerina; Sikinioti-Lock, Alexandra; Hajdu, Kata; Aggelopoulos, Christos

    2016-09-01

    A variety of aqueous suspensions (nanofluids) of zero-valent nano-particles (nZVI) are prepared by wet chemistry techniques, their stability and longevity is evaluated by physic-chemical methods of characterization, and their reactivity toward the dechlorination of per-chloro-ethylene (PCE) is examined with tests in batch reactors. For assessing the mobility, longevity and reactivity of nZVI suspensions (nanofluids), under flow-through conditions, visualization multiphase flow and transport tests are performed on a glass-etched pore network. The nZVI breakthrough curves are constructed by measuring the transient variation of the iron concentration in the effluent with atomic absorption spectroscopy. The capacity of nZVI to remediate the bulk phase of PCE is quantified by detecting the mass loss rate of PCE ganglia trapped in glass-etched pore networks during the continuous injection of nZVI suspension or pure water. The nZVI injection in porous media is simulated as an advection- dispersion process by accounting for the attachment/detachment of nanoparticles on the pore-walls, and describing the kinetics of PCE dissolution and reaction by 1st order equations. Visualization experiments reveal that the gradual elimination of PCE ganglia by the injected nZVI is associated with the preferential "erosion" of the upstream interfacial regions. The step controlling the overall process kinetics might be either (i) the enhanced PCE dissolution or (ii) the direct reaction of bulk PCE with the nZVI deposited upon the ganglia interfaces. Inverse modeling of the experiments under the simplifying assumption of one active mechanism indicates that the estimated kinetic coefficients are increasing functions of the flow rate. PMID:26875604

  7. Quantification of changes in zero valent iron morphology using X-ray computed tomography.

    PubMed

    Luo, Ping; Bailey, Elizabeth H; Mooney, Sacha J

    2013-11-01

    Morphological changes within the porous architecture of laboratory scale zero valent iron (ZVI) permeable reactive barriers (PRBs), after exposure to different groundwater conditions, have been quantified experimentally for different ZVI/sand ratios (10%, 50% and 100%, W/W) with the aim of inferring porosity changes in field barriers. Column studies were conducted to simulate interaction with different water chemistries, a synthetic groundwater, acidic drainage and deionised (DI) water as control. Morphological changes, in terms of pore size and distribution, were measured using X-ray computed tomography (CT). CT image analysis revealed significant morphological changes in columns treated with different water chemistries. For example, 100% ZVI (W/W) columns had a higher frequency of small pores (0.6 mm) was observed in ZVI grains reacted with typical groundwater, resulting in a porosity of 27%, compared to 32% when exposed to DI water. In comparison, ZVI grains treated with the acidic drainage had higher porosity (44%) and larger average pore size (2.8 mm). 10% ZVI PRB barrier material had the highest mean porosity (56%) after exposure to any water chemistry whilst 100% ZVI (W/W) columns always had the lowest (34%) with the 50% ZVI (W/W) in between (40%). These results agree with previously published PRB field data and simultaneously conducted geochemical monitoring and mass balance calculation, indicating that both the geochemical and hydraulic environment of the PRB play an important role in determining barrier lifespan. This study suggests that X-ray CT image analysis is a powerful tool for studying the detailed inter pores between ZVI grains within PRBs. PMID:24552065

  8. 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. PMID:25072767

  9. ZERO-VALENT IRON REMOVAL RATES OF AQUEOUS Cr(VI) MEASURED UNDER FLOW CONDITIONS

    SciTech Connect

    Kaplan, Daniel I.; Gilmore, Tyler J.

    2004-06-01

    The rates of Cr(VI) removal from the aqueous phase by zero-valent iron, Fe(0), was measured under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a groundwater remediation technology that replaces the sand in a filter pack of a conventional well with a reactive material, such as Fe(0). Dissolved Cr(VI) concentration, dissolved O2 concentration, and Eh data indicated that Cr(VI) removal from the aqueous phase was mass-transfer limited. All pseudo-first-order regression fits to the data were significant (P≤0.05), however, they did not capture many of the salient aspects of the data, including that the removal rate often decreased as contact time increased. As such, application of these rate coefficients to predict long-term Cr(VI) removal were compromised. The rate coefficients measured under flow conditions were comparable to those measured previously under batch conditions with significantly greater solution:solid ratios. Between the range of 20 and 100 wt-% Fe(0) in the column, there was little measurable change in the reaction kinetics. Thus, it may be possible to include sand into the reactive filter packs in the event it is necessary to increase filter pack porosity or to decrease the accumulation of secondary reaction products that may lead to filter pack plugging. Background water chemistry (0.2 M NaHCO3, distilled water, and a carbonate-dominated groundwater) had only marginal, if any, effects on reaction rate coefficients. The reaction rates measured in this study indicated that an Fe(0) filter pack could be used to lower Cr(VI) concentrations by several orders of magnitude in a once-through mode of operation of the Reactive Well Technology.

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

    SciTech Connect

    Ding, Yuanzhao; Liu, Bo; Shen, Xin; Zhong, Lirong; Li, Xiqing

    2013-09-01

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

  11. Mechanisms of NOx removal from flue gas by zero valent iron

    SciTech Connect

    Shiao-Shing Chen; Chih-Yu Cheng; Jung-Chun Chang; Chih-Hui Tang

    2006-06-15

    Chemical reaction between nitric oxide (NO) and zero valent iron (ZVI) was studied in a packed-bed column process with high temperatures based on ZVI strong reducing abilities. For six controlled temperatures of 523- 773 K and 400 ppm of NO (typical flue gas temperature and concentration), under short empty bed contact time, NO was completely removed for temperature of 573-773 K but not for 523 K. Breakthrough curves were conducted for the five working temperatures, and the results indicated that NO reductions by ZVI were varied from 2 to 26.7 mg NO/g ZVI. Higher temperature and longer EBCT achieved better NO removal efficiency. X-ray diffraction (XRD) and electron spectroscopy for chemical analysis (ESCA) were conducted to analyze the crystal structure and oxidation state of the reacted ZVI. Three layers of iron species were detected by XRD: ZVI, Fe{sub 3}O{sub 4}, and Fe{sub 2}O{sub 3}. ZVI was the most prevalent species, and Fe{sub 3}O{sub 4} and Fe{sub 2}O{sub 3} were less from the XRD analysis. By ESCA, the oxidation state on the reacted ZVI surface was determined, and the species was identified as Fe{sub 2}O{sub 3}, which is the most oxidizing species for iron. Therefore, three layers from the ZVI core to the ZVI surface can be identified: ZVI, Fe{sub 3}O{sub 4}, and Fe{sub 2}O{sub 3}. Combining the results from XRD and ESCA, the mechanisms for ZVI and NO can be proposed as two consecutive reactions from lower oxidation state (ZVI) in the core to higher oxidation state on the iron surface (Fe{sub 2}O{sub 3}). Because there was only {lt}5% ZVI used to remove NO comparing to theoretical ZVI used based on the proposed stoichiometry, it can be concluded that the heterogeneous reaction only occurred on the ZVI surface instead of on bulk of the ZVI. 11 refs., 8 figs., 3 tabs.

  12. A Case Study of Using Zero-Valent Iron Nanoparticles for Groundwater Remediation

    NASA Astrophysics Data System (ADS)

    Xiong, Z.; Kaback, D.; Bennett, P. J.

    2011-12-01

    Zero-valent iron nanoparticle (nZVI) is a promising technology for rapid in situ remediation of numerous contaminants, including chlorinated solvents, in groundwater and soil. Because of the high specific surface area of nZVI particles, this technology achieves treatment rates that are significantly faster than micron-scale and granular ZVI. However, a key technical challenge facing this technology involves agglomeration of nZVI particles. To improve nZVI mobility/deliverability and reactivity, an innovative method was recently developed using a low-cost and bio-degradable organic polymer as a stabilizer. This nZVI stabilization strategy offers unique advantages including: (1) the organic polymer is cost-effective and "green" (completely bio-compatible), (2) the organic polymer is highly effective in stabilizing nZVI particles; and (3) the stabilizer is applied during particle preparation, making nZVI particles more stable. Through a funding from the U.S. Air Force Center for Engineering and the Environment (AFCEE), AMEC performed a field study to test the effectiveness of this innovative technology for degradation of chlorinated solvents in groundwater at a military site. Laboratory treatability tests were conducted using groundwater samples collected from the test site and results indicated that trichloroethene (main groundwater contaminant at the site) was completely degraded within four hours by nZVI particles. In March and May 2011, two rounds of nZVI injection were performed at the test site. Approximately 700 gallons of nZVI suspension with palladium as a catalyst were successfully prepared in the field and injected into the subsurface. Before injection, membrane filters with a pore size of 450 nm were used to check the nZVI particle size and it was observed that >85% of nZVI particles were passed through the filter based on total iron measurement, indicating particle size of <450 nm. During field injections, nZVI particles were observed in a monitoring well

  13. Effect of coating on the environmental applications of zero valent iron nanoparticles: the lindane case.

    PubMed

    San Román, I; Galdames, A; Alonso, M L; Bartolomé, L; Vilas, J L; Alonso, R M

    2016-09-15

    Commercial stabilized slurry of zero-valent iron nanoparticles (nZVI) as well as laboratory-synthesized polymer-stabilized NZVI nanoparticles were used for lindane (γ-hexachlorocyclohexane) degradation studies in aqueous solution. In the present study, polymer-stabilized iron nanoparticles were stabilized using polyethylene glycol (PEG, Mn ~400 and ~950-1050) and polytetrahydrofuran (PTHF, Mn ~650). To study the effectiveness of the different nanoparticles, a quantitative monitorization of lindane degradation by using solid-phase extraction (SPE) and a qualitative measurement of generated volatile by-products by headspace-solid phase microextraction (HS-SPME) followed by GC/MS were carried out. The obtained data were compared and contrasted with the results obtained in previous work. Results showed that the nanoparticles studied in this work possess superior dechlorination performance compared with previous observations. The freshly prepared Fe(0)-PEG400, Fe(0)-PEG1050 and Fe(0)-PTHF exhibited high reactivity during the dechlorination process of lindane in a very short time. The results obtained with the synthesized nanoparticles were similar to those obtained with commercial nanoparticles. However, in all cases reactivity decreased at reaction's late stage. Degradation of lindane by the studied nanoparticles removed 99.9% of the lindane initial concentration after 72h, except for Fe(0)-PTHF nanoparticles, for which the reaction stopped after 5min. In all cases, the reaction followed a second order kinetics. Finally, comparing the results from this study with our previous work, where different nature polymers were considered (Fe(0)-CMC, Fe(0)-PAA and Fe(0)-PAP), more gradual degradation profile of lindane was observed for Fe(0)-PAA and Fe(0)-CMC. It should be noted that in the present case, the reaction of lindane was speeded up with commercial and Fe(0)-PEG nanoparticles. Nevertheless, in the later case, the composition of by-products was affected by the presence

  14. Synergistic degradation of chlorinated hydrocarbons with microorganisms and zero valent iron

    NASA Astrophysics Data System (ADS)

    Schöftner, Philipp; Summer, Dorothea; Leitner, Simon; Watzinger, Andrea; Wimmer, Bernhard; Reichenauer, Thomas

    2016-04-01

    Sites contaminated with chlorinated hydrocarbons (CHC) are located mainly within build-up regions. Therefore in most cases only in-situ technologies without excavation of soil material can be used for remediation. This project examines a novel in-situ remediation method, in which the biotic degradation via bacteria is combined with abiotic degradation via zero-valent iron particles (ZVI). ZVI particles are injected into the aquifer where CHC-molecules are reductively dechlorinated. However Fe0 is also oxidized by reaction with water leading to generation of H2 without any CHC degradation. To achieve biotic degradation often strictly anaerobic strains of the bacteria Dehalococcoides are used. These bacteria can dechlorinate CHC by utilizing H2. By combining these processes the H2, produced during the anaerobic corrosion of Fe0, could be used by bacteria for further CHC degradation. Therefore the amount of used Fe0 and as a consequence also remediation costs could be reduced. Additionally the continuous supply of H2 could make the bacterial degradation more controllable. Different Fe0 particles (nano- and micro-scale) were tested for their perchloroethene (PCE) degradation rate and H2 production rate in microcosms. PCE-degradation rate by different bacterial cultures was investigated in the same microcosm system. In course of these experiments the 13C enrichment factors of the PCE degradation of the different particles and cultures were determined to enable the differentiation of biotic and abiotic degradation. Preliminary results showed, that the nano-scale particles reacted faster with PCE and water than their micro-scaled counterparts. The PCE degradation via micro-scaled particles lead to 13C enrichment factors in the range of -3,6 ‰ ± 0,6 to -9,5 ‰ ± 0,2. With one of the examined bacterial cultures a fast reduction of PCE to ethene was observed. Although PCE and TCE were completely degraded by this culture the metabolites DCE and VC could still be detected

  15. Influence of fulvic acid on the colloidal stability and reactivity of nanoscale zero-valent iron.

    PubMed

    Dong, Haoran; Ahmad, Kito; Zeng, Guangming; Li, Zhongwu; Chen, Guiqiu; He, Qi; Xie, Yankai; Wu, Yanan; Zhao, Feng; Zeng, Yalan

    2016-04-01

    This study investigated the effect of fulvic acid (FA) on the colloidal stability and reactivity of nano zero-valent iron (nZVI) at pH 5, 7 and 9. The sedimentation behavior of nZVI differed at different pH. A biphasic model was used to describe the two time-dependent settling processes (i.e., a rapid settling followed by a slower settling) and the settling rates were calculated. Generally, the settling of nZVI was more significant at the point of zero charge (pHpzc), which could be varied in the presence of FA due to the adsorption of FA on the nZVI surface. More FA was adsorbed on the nZVI surface at pH 5-7 than pH 9, resulting in the varying sedimentation behavior of nZVI via influencing the electrostatic repulsion among particles. Moreover, it was found that there was a tradeoff between the stabilization and the reactivity of nZVI as affected by the presence of FA. When FA concentration was at a low level, the adsorption of FA on the nZVI surface could enhance the particle stabilization, and thus facilitating the Cr(VI) reduction by providing more available surface sites. However, when the FA concentrations were too high to occupy the active surface sites of nZVI, the Cr(VI) reduction could be decreased even though the FA enhanced the dispersion of nZVI particles. At pH 9, the FA improved the Cr(VI) reduction by nZVI. Given the adsorption of FA on the nZVI surface was insignificant and its effect on the settling behavior of nZVI particles was minimal, it was proposed that the FA formed soluble complexes with the produced Fe(III)/Cr(III) ions, and thus reducing the degree of passivation on the nZVI surface and facilitating the Cr(VI) reduction. PMID:26796746

  16. Degradation of Perchloroethene by zero-valent iron evaluated by carbon isotope fractionation

    NASA Astrophysics Data System (ADS)

    Leitner, Simon; Watzinger, Andrea; Reichenauer, Thomas G.

    2014-05-01

    Perchloroethene (PCE) is a widely spread groundwater contaminant in formally used industrial sites. Zero valent iron (ZVI) is used for in situ chemical reduction (ISCR) of PCE contaminants in the groundwater. A key factor in the application of in situ remediation technologies is a proper monitoring of contaminant reduction. The measurement of the stable isotope ratio is a promising method that is already used for quantifying microbial degradation of chlorinated contaminants. The carbon isotope ratio of PCE, measured by - isotope ratio mass spectrometry coupled to a gas chromatograph via a combustion interface (GC-C-IRMS), increases during degradation of PCE and can be directly related to the degree of degradation. It can be used to directly quantify chemical degradation and thus serves as a useful monitoring tool for groundwater remediation. An experiment to determine the carbon isotopic fractionation factor was performed as a lab experiment using Nanofer Star (NANOIRON). Two different PCE concentrations (c1: 220mgL-1, c2: 110mgL-1) mixed with 0.5 g of ZVI were sealed under deoxygenated conditions in 250 ml glas bottles locked with mininert caps. The bottles were incubated on a shaker for 865 h. Samples were taken weekly to measure the change in the carbon isotopic ratio of PCE as well as its concentration. Results showed a strong increase in the carbon isotope ratio (δ-value) of PCE (start: -27 o end: -4 ), which indicates a significant dechlorination process of PCE. Beside PCE also one degradation product (Trichloroethylene - TCE) was measured. TCE was further dechlorinated as indicated by the δ-value change of TCE from -26 o to -4 oȦn unexpected intermediate value of -45 o for TCE was observed in the experiment. This fluctuation could be induced by the time depending concentration due to degradation and conversation processes. Furthermore, it seems that the progress of the δ-value is affected by the starting concentration of PCE (δ-value of c1 < c2) as

  17. Removal of Arsenic(III) from Groundwater with Nano Scale Zero-Valent Iron

    NASA Astrophysics Data System (ADS)

    Manning, B. A.; Kiser, J.; Kanel, S. R.; Choi, H.

    2004-12-01

    Arsenite (As(III)) is a highly toxic, soluble species that is a naturally occurring groundwater contaminant of environmental concern. There is a need for detailed information about the natural geochemical cycling of As(III), including the fundamental chemical mechanisms of the reactions of As(III) with a variety of surfaces, both natural and engineered. In this paper we focus on the development of ultra-fine, synthetic nanoscale zero-valent iron (nano-Fe(0)) material as both a potential candidate for As(III) remediation and a high surface area model compound to study the remediation of groundwater containing As(III) with larger Fe(0) particles. A variety of techniques were used including SEM, AFM, XRD, and X-ray absorption spectroscopy (XAS) to characterize particle size, surface morphology, corrosion layers formed, and As(III)-nano-Fe(0) surface complexation chemistry. Results from AFM showed particle size ranged from 1-120 nm. XRD and SEM results revealed that nano-Fe(0) gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) batch adsorption kinetics were rapid following a pseudo-first-order rate expression with observed reaction rate constants (kobs) of up to 1.3 per min (at varying Fe(0) densities). These values are about 1000 times higher than kobs literature values for As(III) adsorption on micron size Fe(0). Results from laser light scattering (electrophoretic mobility) and XAS confirmed that inner-sphere surface complexation occurred on nano-Fe(0) corrosion products. In addition, oxidation of As(III) to As(V) was evident in batch experiments. Addition of 10 mM anions (bicarbonate, sulfate, nitrate, and arsenate) had no effect on the uptake of As(III) whereas 10 mM silicic acid and phosphate reduced the uptake of As(III) from 99.9% to 44.9 and 66.3%, respectively. Our results suggest that nano-Fe(0) is an appropriate material for further investigation of the feasibility of using Fe(0) for As

  18. Effect of accelerated carbonation and zero valent iron on metal leaching from bottom ash.

    PubMed

    Nilsson, M; Andreas, L; Lagerkvist, A

    2016-05-01

    About 85% of the ashes produced in Sweden originated from the incineration of municipal solid waste and biofuel. The rest comes from the thermal treatment of recycled wood, peat, charcoal and others. About 68% of all ashes annually produced in Sweden are used for constructions on landfills, mainly slopes, roads and embankments, and only 3% for construction of roads and working surfaces outside the landfills (SCB, 2013). Since waste bottom ash (BA) often has similar properties to crushed bedrock or gravel, it could be used for road constructions to a larger extent. However, the leaching of e.g. Cr, Cu, Mo, Pb and Zn can cause a threat to the surrounding environment if the material is used as it is. Carbonation is a commonly used pre-treatment method, yet it is not always sufficient. As leaching from aged ash is often controlled by adsorption to iron oxides, increasing the number of Fe oxide sorption sites can be a way to control the leaching of several critical elements. The importance of iron oxides as sorption sites for metals is known from both mineralogical studies of bottom ash and from the remediation of contaminated soil, where iron is used as an amendment. In this study, zero valent iron (Fe(0)) was added prior to accelerated carbonation in order to increase the number of adsorption sites for metals and thereby reduce leaching. Batch, column and pHstat leaching tests were performed and the leaching behaviour was evaluated with multivariate data analysis. It showed that leaching changed distinctly after the tested treatments, in particular after the combined treatment. Especially, the leaching of Cr and Cu clearly decreased as a result of accelerated carbonation. The combination of accelerated carbonation with Fe(0) addition reduced the leaching of Cr and Cu even further and reduced also the leaching of Mo, Zn, Pb and Cd compared to untreated BA. Compared with only accelerated carbonation, the Fe(0) addition significantly reduced the leaching of Cr, Cu and Mo

  19. Degradation of simazine from aqueous solutions by diatomite-supported nanosized zero-valent iron composite materials.

    PubMed

    Sun, Zhiming; Zheng, Shuilin; Ayoko, Godwin A; Frost, Ray L; Xi, Yunfei

    2013-12-15

    A novel composite material based on deposition of nanosized zero-valent iron (nZVI) particles on acid-leached diatomite was synthesised for the removal of a chlorinated contaminant in water. The nZVI/diatomite composites were characterised by X-ray diffraction, scanning electron microscopy, elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Compared with the pure nZVI particles, better dispersion of nZVI particles on the surface or inside the pores of diatom shells was observed. The herbicide simazine was selected as the model chlorinated contaminant and the removal efficiency by nZVI/diatomite composite was compared with that of the pristine nZVI and commercial iron powder. It was found that the diatomite supported nZVI composite material prepared by centrifugation exhibits relatively better efficient activity in decomposition of simazine than commercial Fe, lab synthesised nZVI and composite material prepared via rotary evaporation, and the optimum experimental conditions were obtained based on a series of batch experiments. This study on immobilising nZVI particles onto diatomite opens a new avenue for the practical application of nZVI and the diatomite-supported nanosized zero-valent iron composite materials have potential applications in environmental remediation. PMID:24231330

  20. Removal of selenium from water with nanoscale zero-valent iron: mechanisms of intraparticle reduction of Se(IV).

    PubMed

    Ling, Lan; Pan, Bingcai; Zhang, Wei-xian

    2015-03-15

    Increasing evidences suggest that nanoscale zero-valent iron (nZVI) is an effective agent for treatment and removal of selenium from water. For example, 1.3 mM selenite was quickly removed from water within 3 min with 5 g/L nZVI. In this work, reaction mechanisms of selenite [Se(IV)] in a single core-shell structured nanoscale zero-valent iron (nZVI) particle were studied with the method of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) integrated with X-ray energy dispersive spectroscopy (XEDS). This method was utilized to visualize solid phase translocation and transformation of Se(IV) such as diffusion, reduction, deposition and the effect of surface defects in a single nanoparticle. Se(IV) was reduced to Se(-II) and Se(0), which then formed a 0.5 nm layer of selenium at the iron oxide-Fe(0) interface at a depth of 6 nm from the surface. The results provided near atomic-resolution proof on the intraparticle diffusion-reduction of Se(IV) induced by nZVI. The STEM mapping also discovered that defects on the surface layer accelerate the diffusion of selenium and increase the capacity of nZVI for selenium sequestration. PMID:25622004

  1. Nanoscale zero-valent iron supported on mesoporous silica: characterization and reactivity for Cr(VI) removal from aqueous solution.

    PubMed

    Petala, Eleni; Dimos, Konstantinos; Douvalis, Alexios; Bakas, Thomas; Tucek, Jiri; Zbořil, Radek; Karakassides, Michael A

    2013-10-15

    MCM-41-supported nanoscale zero-valent iron (nZVI) was sytnhesized by impregnating the mesoporous silica martix with ferric chloride, followed by chemical reduction with NaHB4. The samples were studied with a combination of characterization techniques such as powder X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) and Mössbauer spectroscopy, N2 adsorption measurements, transmission electron microscopy (TEM), magnetization measurements, and thermal analysis methods. The experimental data revealed development of nanoscale zero-valent iron particles with an elliptical shape and a maximum size of ∼80 nm, which were randomly distributed and immobilized on the mesoporous silica surface. Surface area measurements showed that the porous MCM-41 host matrix maintains its hexagonal mesoporous order structure and exhibits a considerable high surface area (609 m(2)/g). Mössbauer and magnetization measurements confirmed the presence of core-shell iron nanoparticles composed of a ferromagnetic metallic core and an oxide/hydroxide shell. The kinetic studies demonstrated a rapid removal of Cr(VI) ions from the aqueous solutions in the presence of these stabilized nZVI particles on MCM-41, and a considerably increased reduction capacity per unit mass of material in comparison to that of unsupported nZVI. The results also indicate a highly pH-dependent reduction efficiency of the material, whereas their kinetics was described by a pseudo-first order kinetic model. PMID:23959249

  2. The influences of iron characteristics, operating conditions and solution chemistry on contaminants removal by zero-valent iron: A review.

    PubMed

    Sun, Yuankui; Li, Jinxiang; Huang, Tinglin; Guan, Xiaohong

    2016-09-01

    For successful application of a zero-valent iron (ZVI) system, of particular interest is the performance of ZVI under various conditions. The current review comprehensively summarizes the potential effects of the major influencing factors, such as iron intrinsic characteristics (e.g., surface area, iron impurities and oxide films), operating conditions (e.g., pH, dissolved oxygen, iron dosage, iron pretreatment, mixing conditions and temperature) and solution chemistry (e.g., anions, cations and natural organic matter) on the performance of ZVI reported in literature. It was demonstrated that all of the factors could exert significant effects on the ZVI performance toward contaminants removal, negatively or positively. Depending on the removal mechanisms of the respective contaminants and other environmental conditions, an individual variable may exhibit different effects. On the other hand, many of these influences have not been well understood or cannot be individually isolated in experimental or natural systems. Thus, more research is required in order to elucidate the exact roles and mechanisms of each factor in affecting the performance of ZVI. Furthermore, based on these understandings, future research may attempt to establish some feasible strategies to minimize the deteriorating effects and utilize the positive effects so as to improve the performance of ZVI. PMID:27206056

  3. Conjunctive effect of CMC-zero-valent iron nanoparticles and FYM in the remediation of chromium-contaminated soils

    NASA Astrophysics Data System (ADS)

    Madhavi, Vemula; Prasad, Tollamadugu Naga Venkata Krishna Vara; Reddy, Balam Ravindra; Reddy, Ambavaram Vijay Bhaskar; Gajulapalle, Madhavi

    2013-04-01

    Chromium is an important industrial metal used in various products and processes but at the same time causing lethal environmental hazards. Remediation of Cr-contaminated soils poses both technological and economic challenges, as conventional methods are often too expensive and difficult to operate. Zero-valent iron particles at nanoscale are proposed to be one of the important reductants of Cr(VI), transforming the same into nontoxic Cr(III). In the present investigation, soils contaminated with Cr(VI) are allowed to react with the various loadings of zero-valent iron nanoparticles (Fe0) for a reaction period of 24 h. Fe0 nanoparticles were synthesized by the reduction of ferrous sulfate in the presence of sodium borohydride and stabilized with carboxy methyl cellulose and were characterized by scanning electron microscopy, energy dispersion spectroscopy, X-ray diffraction, UV-vis spectrophotometer, Fourier transform-infra red spectrophotometer, Raman spectroscopy, dynamic light scattering technique and zeta potential. Further, this work demonstrates the potential utilization of farm yard manure (FYM) and Fe0 nanoparticles in combination and individually for the effective remediation of Cr(VI)-contaminated soils. An increase in the reduction of Cr(VI) from 60 to 80 % was recorded with the increase in the loading of Fe0 nanoparticles from 0.1 to 0.3 mg/100 g individually and in combination with FYM ranging from 50 to 100 mg/100 g soil.

  4. Conjunctive effect of CMC-zero-valent iron nanoparticles and FYM in the remediation of chromium-contaminated soils

    NASA Astrophysics Data System (ADS)

    Madhavi, Vemula; Prasad, Tollamadugu Naga Venkata Krishna Vara; Reddy, Balam Ravindra; Reddy, Ambavaram Vijay Bhaskar; Gajulapalle, Madhavi

    2014-04-01

    Chromium is an important industrial metal used in various products and processes but at the same time causing lethal environmental hazards. Remediation of Cr-contaminated soils poses both technological and economic challenges, as conventional methods are often too expensive and difficult to operate. Zero-valent iron particles at nanoscale are proposed to be one of the important reductants of Cr(VI), transforming the same into nontoxic Cr(III). In the present investigation, soils contaminated with Cr(VI) are allowed to react with the various loadings of zero-valent iron nanoparticles (Fe0) for a reaction period of 24 h. Fe0 nanoparticles were synthesized by the reduction of ferrous sulfate in the presence of sodium borohydride and stabilized with carboxy methyl cellulose and were characterized by scanning electron microscopy, energy dispersion spectroscopy, X-ray diffraction, UV-vis spectrophotometer, Fourier transform-infra red spectrophotometer, Raman spectroscopy, dynamic light scattering technique and zeta potential. Further, this work demonstrates the potential utilization of farm yard manure (FYM) and Fe0 nanoparticles in combination and individually for the effective remediation of Cr(VI)-contaminated soils. An increase in the reduction of Cr(VI) from 60 to 80 % was recorded with the increase in the loading of Fe0 nanoparticles from 0.1 to 0.3 mg/100 g individually and in combination with FYM ranging from 50 to 100 mg/100 g soil.

  5. Degradation of model olive mill contaminants of OMW catalysed by zero-valent iron enhanced with a chelant.

    PubMed

    Sanchez, Irama; Stüber, Frank; Fabregat, Azael; Font, Josep; Fortuny, Agustí; Bengoa, Christophe

    2012-01-15

    The aim of this study was to investigate the effect of a chelated zero valent iron as catalyst on the oxidation of six organic acids that are generally found in olive mill wastewater. The reaction was carried out in a stirred tank reactor under extremely mild conditions, a temperature of 30°C and atmospheric pressure. Solutions of 350 mg/L of the six organic compounds were treated individually using zero valent iron particles (15 g), nitrilotriacetic acid disodium salt (NTA, 100mg/L) and air. The efficiency of the process was evaluated to determine the organic compound conversion, the chemical oxygen demand (COD) reduction and the total organic carbon (TOC) reduction. The caffeic, 4-hydroxyphenylacetic and vanillic acids showed a total conversion after 180, 240 and 300 min of reaction, respectively. In turn, coumaric acid, tyrosol and cinnamic acid only reached conversions of 90, 87 and 68%, respectively, after 360 min of reaction. Four mixtures of the six acids with an initial total concentration of 1000 mg/L were also tested and gave an overall conversion of the organic compounds of 92-99% after 360 min of reaction. The COD conversions of the mixtures were always above 84%, but the TOC conversions values were lower, indicating a poorer mineralization. PMID:22118846

  6. Removing pentachlorophenol from water using a nanoscale zero-valent iron/H2O2 system.

    PubMed

    Cheng, Rong; Cheng, Can; Liu, Guo-Hua; Zheng, Xiang; Li, Guanqing; Li, Jie

    2015-12-01

    Nanoscale zero-valent iron (nZVI) is an environmentally benign material that has been widely used as a reducing agent to treat environmental pollutants. In this study, nZVI was used as a heterogeneous Fenton catalyst in an nZVI/H2O2 system to remove pentachlorophenol (PCP) from water. The PCP degradation process in the nZVI/H2O2 system was completed within 1h. The relative Cl(-) concentration increased throughout the test period (6h), indicating that the performance of the oxidative system in terms of dechlorination was excellent. The initial H2O2 concentration significantly influenced the PCP removal rate, and nZVI performed better than commercial zero-valent iron as a catalyst. Moreover, magnetite (Fe3O4), which was the main product of the corrosion of nZVI, was found to perform well as an adsorbent and catalyst, so it allowed the nZVI to be effectively reused. PMID:26184790

  7. Arsenic chemistry with sulfide, pyrite, zero-valent iron, and magnetite

    NASA Astrophysics Data System (ADS)

    Sun, Fenglong

    The aim of this thesis is to study the immobilization reactions of arsenic in water. Since compounds containing iron or sulfide are common in most natural and engineered systems, the research focused on the redox reactions and adsorption of arsenic with sulfide, pyrite, zero-valent iron (ZVI), and magnetite which were studied through wet chemistry methods and spectroscopic techniques. The kinetic and thermodynamic information of the reactions of As(V) with S(-II), As(V)/As(III) with pyrite and surface-oxidized pyrite, As(V) with ZVI and acid-treated ZVI, As(III) with magnetite was used to identify mechanisms. The necessity to maintain strictly anoxic conditions was emphasized for the study of arsenic redox chemistry with sulfides and ZVI. The major findings of this research can be stated as follows. First, dissolved sulfide reduced As(V) to lower valences to form a yellow precipitate at acidic pH. The reaction involved the formation of thioarsenic intermediate species. Dissolved O2, granular activated carbon (GAC) and dissolved Fe(II) inhibited the removal of As(V) by sulfide. Elemental sulfur catalyzed the reduction of As(V) by sulfide, which implied the possible benefit of using sulfur-loaded GAC for arsenic removal. Possible reaction mechanisms were discussed. Second, As(III) adsorbed on pristine pyrite over a broader pH range than on surface-oxidized pyrite, while As(V) adsorbed over a narrower pH range with pristine pyrite. As(V) was completely reduced to As(III) on pristine pyrite at acidic pH but not at higher pH. The reduction was first-order with respect to As(V). As(V) was not reduced on surface-oxidized pyrite at pH = 4--11. The different behaviors of As(V) and As(III) on pristine and surface oxidized pyrite determines the toxicity and mobility of arsenic under oxic/anoxic environments. Third, commercial ZVI reduced As(V) to As(III) at low pH (<9) but not at higher pH. Acid-treated ZVI reduced As(V) to As(0), indicated by wet chemical analyses and by

  8. In situ remediation of ground water contaminated with chromate and chlorinated solvents using zero-valent iron: A field study

    SciTech Connect

    Puls, R.W.; Paul, C.J.; Powell, R.W.

    1995-12-01

    A small-scale field test was recently initiated to evaluate the in situ remediation of ground water contaminated with chromate and chlorinated organics using a permeable reactive barrier. The barrier was composed of an iron metal-coarse sand-native aquifer solid mixture, and was installed using a staggered {open_quotes}fence{close_quotes} design through large hollow-stem augers. The objectives of the project were to evaluate the ability of the cylinders or {open_quotes}fence posts{close_quotes} to remove contaminants from solution immediately downgradient and adjacent to the iron cylinders, evaluate the resultant changes in aqueous geochemistry induced by the presence of the zero-valent iron, and identify chemical, physical and biological processes which may affect long-term performance of such remedial technologies.

  9. 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

  10. EFFECTS OF NATURAL ORGANIC MATTER, ANTHROPOGENIC SURFACTANTS, AND MODEL QUINONES ON THE REDUCTION OF CONTAMINANTS BY ZERO-VALENT IRON. (R827117)

    EPA Science Inventory

    Recent studies of contaminant reduction by zero-valent iron metal (Fe0) have highlighted the role of iron oxides at the metal–water interface and the effect that sorption has at the oxide–water interface on contaminant reduction kinetics. The results s...

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

    PubMed

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

    2015-10-01

    The application of nanoscale zero-valent iron (nZVI) for subsurface remediation of groundwater contaminants is a promising new technology, which can be understood as alternative to the permeable reactive barrier technique using granular iron. Dechlorination of organic contaminants by zero-valent iron seems promising. Currently, one limitation to widespread deployment is the fast agglomeration and sedimentation of nZVI in colloidal suspensions, even more so when in soils and sediments, which limits the applicability for the treatment of sources and plumes of contamination. Colloid-supported nZVI shows promising characteristics to overcome these limitations. Mobility of Carbo-Iron Colloids (CIC) - a newly developed composite material based on finely ground activated carbon as a carrier for nZVI - was tested in a field application: In this study, a horizontal dipole flow field was established between two wells separated by 5.3m in a confined, natural aquifer. The injection/extraction rate was 500L/h. Approximately 1.2kg of CIC was suspended with the polyanionic stabilizer carboxymethyl cellulose. The suspension was introduced into the aquifer at the injection well. Breakthrough of CIC was observed visually and based on total particle and iron concentrations detected in samples from the extraction well. Filtration of water samples revealed a particle breakthrough of about 12% of the amount introduced. This demonstrates high mobility of CIC particles and we suggest that nZVI carried on CIC can be used for contaminant plume remediation by in-situ formation of reactive barriers. PMID:25864966

  12. 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.

  13. 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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  14. ENVIRONMENTAL RESEARCH BRIEF: LONG-TERM PERFORMANCE OF PERMEABLE REACTIVE BARRIERS USING ZERO-VALENT IRON: AN EVALUATION AT TWO SITES

    EPA Science Inventory

    Geochemical and microbiological factors that control long-term performance of subsurface permeable reactive barriers were evaluated at the Elizabeth City, NC and the Denver Federal Center, CO sites. These groundwater treatment systems use zero-valent iron filings to intercept an...

  15. Zero-valent iron/biotic treatment system for perchlorate-contaminated water: lab-scale performance, modeling, and full-scale implications

    EPA Science Inventory

    The computer program AQUASIM was used to model biological treatment of perchlorate-contaminated water using zero-valent iron corrosion as the hydrogen gas source. The laboratory-scale column was seeded with an autohydrogenotrophic microbial consortium previously shown to degrade ...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  17. 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.

  18. Enhanced removal of soluble Cr(VI) by using zero-valent iron composite supported by surfactant-modified zeolites.

    PubMed

    Dang, Hongyu; Zhang, Yongxiang; Du, Peiwen

    2014-01-01

    Zero-valent iron (ZVI) was immobilized onto surfactant-modified zeolites (SMZ) using calcium alginate. Scanning electron microscopy showed that ZVI powder was uniformly immobilized on the surface of the SMZ. The added ZVI powder resulted in enhanced dichromate removal efficiency and the heterogeneous surface of the composite. The adsorption of dichromate onto the ZVI-SMZ composites fitted well to a pseudo-second-order model and the Langmuir adsorption isotherm. The maximum dichromate adsorption capacity of the composite was 2.49 mg/g at the temperature of 293 K. Higher removal efficiency was obtained at pH lower than 7. X-ray photoelectron spectrometry revealed that the composites combined the strong reductive quality of ZVI and superior adsorption of SMZ. PMID:25353946

  19. Long-term performance of permeable reactive barriers using zero-valent iron: geochemical and microbiological effects.

    PubMed

    Wilkin, Richard T; Puls, Robert W; Sewell, Guy W

    2003-01-01

    Geochemical and microbiological factors that control long-term performance of subsurface permeable reactive barriers were evaluated at the Elizabeth City, North Carolina, and the Denver Federal Center, Colorado, sites. These ground water treatment systems use zero-valent iron filings (Peerless Metal Powders Inc.) to intercept and remediate chlorinated hydrocarbon compounds at the Denver Federal Center (funnel-and-gate system) and overlapping plumes of hexavalent chromium and chlorinated hydrocarbons at Elizabeth City (continuous wall system). Zero-valent iron at both sites is a long-term sink for carbon, sulfur, calcium, silicon, nitrogen, and magnesium. After about four years of operation, the average rates of inorganic carbon (IC) and sulfur (S) accumulation are 0.09 and 0.02 kg/m2/year, respectively, at Elizabeth City where upgradient waters contain <400 mg/L of total dissolved solids (TDS). At the Denver Federal Center site, upgradient ground water contains 1000 to 1200 mg/L TDS and rates of IC and S accumulation are as high as 2.16 and 0.80 kg/m2/year, respectively. At both sites, consistent patterns of spatially variable mineral precipitation and microbial activity are observed. Mineral precipitates and microbial biomass accumulate the fastest near the upgradient aquifer-Fe0 interface. Maximum net reductions in porosity due to the accumulation of sulfur and inorganic carbon precipitates range from 0.032 at Elizabeth City to 0.062 at the Denver Federal Center (gate 2) after about four years. Although pore space has been lost due the accumulation of authigenic components, neither site shows evidence of pervasive pore clogging after four years of operation. PMID:12873012

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

    NASA Astrophysics Data System (ADS)

    Dai, C.; Zhang, Y.

    2015-12-01

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

  1. Generation of Oxidants From the Reaction of Nanoparticulate Zero-Valent Iron and Oxygen for the use in Contaminant Remediation

    NASA Astrophysics Data System (ADS)

    Keenan, C. R.; Lee, C.; Sedlak, D. L.

    2007-12-01

    The reaction of zero-valent iron (ZVI) with oxygen can lead to the formation of oxidants, which may be used to transform recalcitrant contaminants including non-polar organics and certain metals. Nanoparticulate iron might provide a practical mechanism of remediating oxygen-containing groundwater and contaminated soil. To gain insight into the reaction mechanism and to quantify the yield of oxidants, experiments were performed with model organic compounds in the presence of nanoparticulate zero-valent iron and oxygen. At pH values below 5, ZVI nanoparticles were oxidized within 30 minutes with a stoichiometry of approximately two Fe0 oxidized per O2 consumed. Using the oxidation of methanol and ethanol to formaldehyde and acetaldehyde, respectively, we found that less than 2% of the consumed oxygen was converted to reactive oxidants under acidic conditions. The yield of aldehydes increased with pH up to pH 7, with maximum oxidant yields of around 5% relative to the mass of ZVI added. The increase of aldehyde yield with pH was attributable to changes in the processes responsible for oxidant production. At pH values below 5, the corrosion of ZVI by oxygen produces hydrogen peroxide, which subsequently reacts with ferrous iron [Fe(II)] via the Fenton reaction. At higher pH values, the aldehydes are produced when Fe(II), the initial product of ZVI oxidation, reacts with oxygen. The decrease in oxidant yield at pH values above 7 may be attributable to precipitation of Fe(II). The oxidation of benzoic acid and 2-propanol to para-hydroxybenzoic acid and acetone, respectively, followed a very different trend compared to the primary alcohols. In both cases, the highest product yields (approximately 2% with respect to ZVI added) were observed at pH 3. Yields decreased with increasing pH, with no oxidized product detected at neutral pH. These results suggest that two different oxidants may be produced by the system: hydroxyl radical (OH-·) at acidic pH and a more selective

  2. Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

    PubMed Central

    Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

    2015-01-01

    Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system. PMID:25652244

  3. Zero Valent Iron Significantly Enhances Methane Production from Waste Activated Sludge by Improving Biochemical Methane Potential Rather Than Hydrolysis Rate

    NASA Astrophysics Data System (ADS)

    Liu, Yiwen; Wang, Qilin; Zhang, Yaobin; Ni, Bing-Jie

    2015-02-01

    Anaerobic digestion has been widely applied for waste activated sludge (WAS) treatment. However, methane production from anaerobic digestion of WAS is usually limited by the slow hydrolysis rate and/or poor biochemical methane potential of WAS. This work systematically studied the effects of three different types of zero valent iron (i.e., iron powder, clean scrap and rusty scrap) on methane production from WAS in anaerobic digestion, by using both experimental and mathematical approaches. The results demonstrated that both the clean and the rusty iron scrap were more effective than the iron powder for improving methane production from WAS. Model-based analysis showed that ZVI addition significantly enhanced methane production from WAS through improving the biochemical methane potential of WAS rather than its hydrolysis rate. Economic analysis indicated that the ZVI-based technology for enhancing methane production from WAS is economically attractive, particularly considering that iron scrap can be freely acquired from industrial waste. Based on these results, the ZVI-based anaerobic digestion process of this work could be easily integrated with the conventional chemical phosphorus removal process in wastewater treatment plant to form a cost-effective and environment-friendly approach, enabling maximum resource recovery/reuse while achieving enhanced methane production in wastewater treatment system.

  4. Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation.

    PubMed

    Schäfer, Dirk; Köber, Ralf; Dahmke, Andreas

    2003-09-01

    The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Schäfer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of

  5. Removal of hexavalent chromium from aqueous solutions using micro zero-valent iron supported by bentonite layer.

    PubMed

    Daoud, Waseem; Ebadi, Taghi; Fahimifar, Ahmad

    2015-01-01

    Hexavalent chromium Cr(VI) is of particular environmental concern due to its toxicity, mobility, and challenging removal from industrial wastewater. It is a strong oxidizing agent that is carcinogenic and mutagenic and diffuses quickly through soil and aquatic environments. Moreover, it does not form insoluble compounds in aqueous solutions; therefore, separation by precipitation is not feasible. While Cr(VI) oxyanions are very mobile and toxic in the environment, trivalent Cr(III) cations are the opposite and, like many metal cations, Cr(III) forms insoluble precipitates. Thus, reducing Cr(VI)-Cr(III) simplifies its removal from effluent and also reduces its toxicity and mobility. Permeable reactive barriers (PRBs) with zero-valent iron (ZVI) have been used to remediate contaminated groundwater with metals, but using ZVI in remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation, and difficulty in separation of iron from the treated solution. Thus, the technology used in the present study is developed to address these problems by placing a layer of bentonite after the PRB layer to remove iron from the treated water. The removal rates of Cr(VI) under different values of pH were investigated, and the results indicated the highest adsorption capacity at low pH. PMID:25768212

  6. 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. PMID:26006292

  7. Hexavalent chromium reduction in contaminated soil: A comparison between ferrous sulphate and nanoscale zero-valent iron.

    PubMed

    Di Palma, L; Gueye, M T; Petrucci, E

    2015-01-01

    Iron sulphate (FeSO4) and colloidal nano zero-valent iron (nZVI) as reducing agents were compared, with the aim of assessing their effectiveness in hexavalent chromium [Cr(VI)] removal from a contaminated industrial soil. Experiments were performed on soil samples collected from an industrial site where a nickel contamination, caused by a long-term productive activity, was also verified. The influence of reducing agents amount with respect to chromium content and the effectiveness of deoxygenation of the slurry were discussed. The soil was fully characterized before and after each test, and sequential extractions were performed to assess chemico-physical modifications and evaluate metals mobility induced by washing. Results show that both the reducing agents successfully lowered the amount of Cr(VI) in the soil below the threshold allowed by Italian Environmental Regulation for industrial reuse. Cr(VI) reduction by colloidal nZVI proved to be faster and more effective: the civil reuse of soil [Cr(VI)<2mg/kg] was only achieved using colloidal nZVI within 60min adopting a nZVI/Cr(VI) molar ratio of 30. The reducing treatment resulted in an increase in the amount of chromium in the oxide-hydroxide fraction, thus confirming a mechanism of chromium-iron hydroxides precipitation. In addition, a decrease of nickel (Ni) and lead (Pb) content in soil was also observed when acidic conditions were established. PMID:25139286

  8. Application of Zero-Valent Iron Nanoparticles for the Removal of Aqueous Zinc Ions under Various Experimental Conditions

    PubMed Central

    Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2014-01-01

    Application of zero-valent iron nanoparticles (nZVI) for Zn2+ removal and its mechanism were discussed. It demonstrated that the uptake of Zn2+ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn2+ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn2+ removal by nZVI. The DO enhanced the removal efficiency of Zn2+. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn2+ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn2+ by nZVI because the existing H+ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn2+ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn2+ were higher than Cd2+. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn2+. PMID:24416439

  9. Efficient removal of uranium from aqueous solution by zero-valent iron nanoparticle and its graphene composite.

    PubMed

    Li, Zi-Jie; Wang, Lin; Yuan, Li-Yong; Xiao, Cheng-Liang; Mei, Lei; Zheng, Li-Rong; Zhang, Jing; Yang, Ju-Hua; Zhao, Yu-Liang; Zhu, Zhen-Tai; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-06-15

    Zero-valent iron nanoparticle (ZVI-np) and its graphene composites were prepared and applied in the removal of uranium under anoxic conditions. It was found that solutions containing 24 ppm U(VI) could be completely cleaned up by ZVI-nps, regardless of the presence of NaHCO3, humic acid, mimic groundwater constituents or the change of solution pH from 5 to 9, manifesting the promising potential of this reactive material in permeable reactive barrier (PRB) to remediate uranium-contaminated groundwater. In the measurement of maximum sorption capacity, removal efficiency of uranium kept at 100% until C0(U) = 643 ppm, and the saturation sorption of 8173 mg U/g ZVI-nps was achieved at C0(U) = 714 ppm. In addition, reaction mechanisms were clarified based on the results of SEM, XRD, XANES, and chemical leaching in (NH4)2CO3 solution. Partially reductive precipitation of U(VI) as U3O7 was prevalent when sufficient iron was available; nevertheless, hydrolysis precipitation of U(VI) on surface would be predominant as iron got insufficient, characterized by releases of Fe(2+) ions. The dissolution of Fe(0) cores was assigned to be the driving force of continuous formation of U(VI) (hydr)oxide. The incorporation of graphene supporting matrix was found to facilitate faster removal rate and higher U(VI) reduction ratio, thus benefitting the long-term immobilization of uranium in geochemical environment. PMID:25734531

  10. 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

    2016-05-01

    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.

  11. Comparison of Iron Sulfide and Zero-Valent Iron as Reactive Materials for the Removal of Arsenic From Groundwater

    NASA Astrophysics Data System (ADS)

    Henderson, A. D.; Demond, A. H.

    2007-12-01

    Zero-valent iron (ZVI) installed in permeable reactive barriers (PRBs) has been shown to be an effective remediation agent for several contaminants, including arsenic (As), a redox-active oxyanion present in reduced form as arsenite, AsO3(3-), and in oxidized form as arsenate, AsO4(3-). Work performed has shown greater removal of arsenic by iron sulfide (FeS), as mackinawite, than by ZVI under anaerobic conditions, recommending the use of FeS in PRB systems. For both ZVI and FeS PRB systems, the interaction of the reactive porous media with groundwater species, and calcium and carbonate in particular, is key to maintaining the permeability and reactivity of the PRB, both of which are necessary for continued treatment. If geochemical conditions are favorable, CaCO3(s) may precipitate, thus reducing permeability and passivating the reactive surface, preventing further remediation. In a statistical review of field PRB performance (Henderson and Demond, Env. Eng. Sci., 2007), it was found that alkalinity, as an indicator of the potential for precipitation of carbonate solids, was correlated to increased risk of PRB failure. A combination of experimental and geochemical modeling approaches is being used to investigate the quantity of calcium carbonate formation in anaerobic FeS and ZVI systems. Column tests with FeS to date have resulted in behavior unlike that observed with ZVI. In the ZVI columns, a pH increase has allowed the precipitation of CaCO3(s), which led to a reduction in permeability. In the FeS columns, the effluent pH and aqueous calcium concentrations were essentially the same as the influent, suggesting that the buffer capacity of carbonate prevented a pH increase, thus precluding the precipitation of CaCO3(s). Geochemical modeling suggests that the interaction of carbonate and FeS may self-regulate in PRB systems: at high carbonate concentrations, when the precipitation of CaCO3(s) could reduce permeability, the buffer capacity provided by the carbonate

  12. Facile synthesis of graphene nano zero-valent iron composites and their efficient removal of trichloronitromethane from drinking water.

    PubMed

    Chen, Haifeng; Cao, Yu; Wei, Enze; Gong, Tingting; Xian, Qiming

    2016-03-01

    Halonitromethanes (HNMs), as an emerging class of disinfection by-products containing nitrogen (N-DBPs) in drinking water, have possessed public health concerns. Two most studied materials, graphene and nanometer-sized zero-valent iron, have been successfully combined into binary nanocomposites (G-nZVI) via facile carbonization and calcinations of glucose and ferric chloride, which was used in the removal of HNMs from drinking water in this study. When the Fe/C mass ratio was 1:5, the as-prepared G-nZVI hybrids comprised numerous dispersed Fe(0) nanoparticles with a range of 5-10 nm in diameter. Batch experimental results indicated that the as-prepared G-nZVI could effectively remove trichloronitromethane (TCNM), a dominant in the group of HNMs from drinking water. About 99% of initial TCNM could be adsorbed and degraded under 60 mg/L G-nZVI dosage within 120 min. Kinetic studies indicated that the removal of TCNM by G-nZVI followed a pseudo first order rate (R(2) > 0.9). The degradation pathways of TCNM by G-nZVI nanocomposites might include dechlorination and denitration of TCNM. The Fe was in the form of iron oxides in the graphene material shape which was then restored to Fe(0) again via calcinations. These results indicated that the synthesized G-nZVI nanocomposites could be a powerful material to remove HNMs from drinking water. PMID:26706929

  13. 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. PMID:24798898

  14. Simultaneous removal of perchlorate and energetic compounds in munitions wastewater by zero-valent iron and perchlorate-respiring bacteria.

    PubMed

    Ahn, Se Chang; Hubbard, Brian; Cha, Daniel K; Kim, Byung J

    2014-01-01

    Ammonium perchlorate is one of the main constituents in Army's insensitive melt-pour explosive, PAX-21 in addition to RDX and 2,4-dinitroanisole (DNAN). The objective of this study is to develop an innovative treatment process to remove both perchlorate and energetic compounds simultaneously from PAX-21 production wastewater. It was hypothesized that the pretreatment of PAX-21 wastewater with zero-valent iron (ZVI) would convert energetic compounds to products that are more amenable for biological oxidation and that these products serve as electron donors for perchlorate-reducing bacteria. Results of batch ZVI reduction experiments showed that DNAN was completely reduced to 2,4-diaminoanisole and RDX was completely reduced to formaldehyde. Anaerobic batch biodegradation experiments showed that perchlorate (30 mg L(-1)) in ZVI-treated PAX-21 wastewater was decreased to an undetectable level after 5 days. Batch biodegradation experiments also confirmed that formaldehyde in ZVI-treated wastewater was the primary electron donor for perchlorate-respiring bacteria. The integrated iron-anaerobic bioreactor system was effective in completely removing energetic compounds and perchlorate from the PAX-21 wastewater without adding an exogenous electron donor. This study demonstrated that ZVI pretreatment not only removed energetic compounds, but also transformed energetic compounds to products that can serve as the source of electrons for perchlorate-respiring bacteria. PMID:24410688

  15. Mechanism of enhanced nitrate reduction via micro-electrolysis at the powdered zero-valent iron/activated carbon interface.

    PubMed

    Luo, Jinghuan; Song, Guangyu; Liu, Jianyong; Qian, Guangren; Xu, Zhi Ping

    2014-12-01

    Nitrate reduction by zero-valent iron (Fe(0)) powder always works well only at controlled pH lower than 4 due to the formation of iron (hydr)oxides on its surface. Fe(0) powder combined with activated carbon (AC), i.e., Fe(0)/AC micro-electrolysis system, was first introduced to enhance nitrate reduction in aqueous solution. Comparative study was carried out to investigate nitrate reduction by Fe(0)/AC system and Fe(0) under near-neutral conditions, showing that the Fe(0)/AC system successfully reduced nitrate even at initial pH 6 with the reduction efficiency of up to 73%, whereas for Fe(0) only ∼10%. The effect of Fe(0) to AC mass ratio on nitrate reduction efficiency was examined. Easier nitrate reduction was achieved with more contact between Fe(0) and AC as the result of decreasing Fe(0) to AC mass ratio. Ferrous ion and oxidation-reduction potential were measured to understand the mechanism of enhanced nitrate reduction by Fe(0)/AC micro-electrolysis. The results suggest that a relative potential difference drives much more electrons from Fe(0) to AC, thus generating adsorbed atomic hydrogen which makes it possible for nitrate to be reduced at near-neural pH. Fe(0)/AC micro-electrolysis thus presents a great potential for practical application in nitrate wastewater treatment without excessive pH adjustment. PMID:25217726

  16. The specific reactive surface area of granular zero-valent iron in metal contaminant removal: Column experiments and modelling.

    PubMed

    Statham, Tom M; Mason, Lachlan R; Mumford, Kathryn A; Stevens, Geoffrey W

    2015-06-15

    A series of dynamic-flow kinetic experiments were conducted to assess the removal rates of aqueous Cu(2+) and Zn(2+) ions by zero-valent iron (ZVI), a promising material for inclusion in cold-climate remediation applications. The influence of experimental parameters on contaminant removal rates, including aqueous flow rate, operating temperature, and the concentrations of ZVI, salt and dissolved oxygen, was investigated. A mass transport model has been developed that accounts (i) aqueous-phase dispersion processes, (ii) film diffusion of contaminant ions to the reactive ZVI surface and (iii) the reactive removal mechanism itself. Regression to the experimental data indicated that when oxygen is present in the solution feed Cu(2+) and Zn(2+) removal processes were limited by film diffusion. In de-aerated solutions film diffusion still controls Cu(2+) removal but a first-order surface reaction provides a better model for Zn(2+) kinetics. Using air as the equilibrium feed gas, the reactive proportion of the total surface area for contaminant removal was calculated to be 97% and 64% of the active spherically-assumed geometric area associated with ZVI media for Cu(2+) and Zn(2+), respectively. Relative to a gas absorption area, determined in previous studies, the reactive proportion is less than 0.41% of the unreacted ZVI total surface area. These findings suggest that only part of the iron oxyhydroxide surface is reacting during ZVI based metal contaminant removal. PMID:25839833

  17. Enhanced ultrasound-assisted degradation of methyl orange and metronidazole by rectorite-supported nanoscale zero-valent iron.

    PubMed

    Yuan, Na; Zhang, Gaoke; Guo, Sheng; Wan, Zhen

    2016-01-01

    In this study, the rectorite-supported nanoscale zero-valent iron (nZVI/R) was synthesized through a reduction method. X-ray diffraction analysis showed the existence of the nZVI in the nZVI/R composite and X-ray photoelectron spectroscopy analysis indicated that the nZVI particles were partly oxidized into iron oxide. Scanning electron microscopy analysis revealed that the nZVI particles were highly dispersed on the surface of the rectorite. The specific surface area of the nZVI/R composite is 21.43 m(2)/g, which was higher than that of rectorite (4.30 m(2)/g) and nZVI (17.97 m(2)/g). In the presence of ultrasound (US), the degradation of methyl orange and metronidazole by the nZVI/R composite was over 93% and 97% within 20 min, respectively, which is much higher than that by the rectorite and the nZVI. The degradation ratio of methyl orange and metronidazole by the nZVI/R composite under US was 1.7 and 1.8 times as high as that by the nZVI/R composite without US, respectively. The mechanism of the enhanced degradation of methyl orange and metronidazole under US irradiation was studied. These results indicate that the US/nZVI/R process has great potential application value for treatment of dye wastewater and medicine wastewater. PMID:26384884

  18. Influences of nanoscale zero valent iron loadings and bicarbonate and calcium concentrations on hydrogen evolution in anaerobic column experiments.

    PubMed

    Paar, Hendrik; Ruhl, Aki Sebastian; Jekel, Martin

    2015-01-01

    The estimation of nanoscale zero-valent iron (nZVI) reactivity after its injection into the subsurface is essential for its application in groundwater remediation. In the present study H₂ generation of commercially available nZVI and novel milled nZVI flakes were investigated in column experiments with varying nZVI loads (ranging from 8 to 43 g nZVI per kg sand). H₂ evolution rates were determined for column experiments without and with hydrogen carbonate and/or calcium. On average 0.29 mmol H₂/L per g Fe⁰ evolved within the first 30 days in column experiments with spherical, commercial nZVI particles. The H₂ evolution developed almost independently of the water matrices applied. The application of nZVI flakes resulted in lower H₂ generation rates. In general corrosion rates accelerated linearly with increasing initial amounts of iron. This was evident in experiments with both particle types. Concentration profiles of carbonate and calcium in influent and effluent were used to estimate corrosion products and precipitates. Despite the presence of high concentrations of inorganic carbon, Fe²⁺ reacted preferably with hydroxide ions to form ferrous hydroxide which is the precursor of magnetite. As a result only minor passivation of the reactive nZVI was observed. PMID:25462777

  19. Aging study on carboxymethyl cellulose-coated zero-valent iron nanoparticles in water: Chemical transformation and structural evolution.

    PubMed

    Dong, Haoran; Zhao, Feng; Zeng, Guangming; Tang, Lin; Fan, Changzheng; Zhang, Lihua; Zeng, Yalan; He, Qi; Xie, Yankai; Wu, Yanan

    2016-07-15

    To assess the long-term fate and the associated risks of nanoscale zero-valent iron (nZVI) used in the water remediation, it is essential to understand the chemical transformations during aging of nZVI in water. This study investigated the compositional and structural evolution of bare nZVI and carboxymethyl cellulose (CMC) coated nZVI in static water over a period of 90 days. Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the corrosion products of nZVI and CMC-nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging, but the coating of CMC could slow down the aging rate of nZVI (as indicated by the slower drop in Fe(0) intensity in XRD pattern). For the bare nZVI, magnetite (Fe3O4) and/or maghemite (γ-Fe2O3) are the dominant corrosion products after 90 days of aging. However, for the CMC-nZVI, the core-shell spheres collapses to acicular-shaped structures after aging with crystalline lepidocrocite (γ-FeOOH) as the primary end product. Moreover, more lepidocrocite present in the corrosion products of CMC-nZVI with higher loading of CMC, which reveals that the CMC coating could influence the transformation of iron oxides. PMID:27037478

  20. Mechanism insights into enhanced trichloroethylene removal using xanthan gum-modified microscale zero-valent iron particles.

    PubMed

    Xin, Jia; Han, Jun; Zheng, Xilai; Shao, Haibing; Kolditz, Olaf

    2015-03-01

    This report focuses on the enhancement in trichloroethylene (TCE) removal from contaminated groundwater using xanthan gum (XG)-modified, microscale, zero-valent iron (mZVI). Compared with bare mZVI, XG-coated mZVI increased the TCE removal efficiency by 30.37% over a 480-h experimental period. Because the TCE removal is attributed to both sorption and reduction processes, the contributions from sorption and reduction were separately investigated to determine the mechanism of XG on TCE removal using mZVI. The results showed that the TCE sorption capacity of mZVI was lower in the presence of XG, whereas the TCE reduction capacity was significantly increased. The FTIR spectra confirmed that XG, which is rich in hydrophilic functional groups, was adsorbed onto the iron surface through intermolecular hydrogen bonds, which competitively repelled the sorption and mass transfer of TCE toward reactive sites. The variations in the pH, Eh, and Fe(2+) concentration as functions of the reaction time were recorded and indicated that XG buffered the solution pH, inhibited surface passivation, and promoted TCE reduction by mZVI. Overall, the XG-modified mZVI was considered to be potentially effective for the in-situ remediation of TCE contaminated groundwater due to its high stability and dechlorination reactivity. PMID:25556871

  1. Degradation of organic dye using zero-valent iron prepared from by-product of pickling line.

    PubMed

    Jung, S C; Cho, H C; Ra, D G; Park, S H; Yoon, H S; Kim, S C; Kim, S J

    2011-01-01

    In this study, zero-valent iron (ZVI) was produced using iron oxide that is a by-product of a pickling line at a steel works. The reaction activity of the produced ZVI was evaluated through a series of decomposition experiments of Orange II aqueous solution. The size of ZVI particles increased with reduction temperature due to coalescence. Correspondingly, the specific surface area of ZVI decreased with increasing reduction temperature. The decomposition efficiency of synthesized ZVI particles was higher at a lower pH. In particular, no significant decomposition reaction was observed at pH of 4 and higher. The rate of the ZVI-assisted decomposition of Orange II was increased by addition of H2O2 at pH of 3, whereas it was reduced by addition of H2O2 at a higher pH of 6. Nevertheless, simultaneous use of ZVI, UV and H2O2 led to a considerable increase in the decomposition rate even at a high pH condition (pH = 6). PMID:22097085

  2. Reduction of chromate from electroplating wastewater from pH 1 to 2 using fluidized zero valent iron process.

    PubMed

    Chen, Shiao-Shing; Cheng, Chih-Yu; Li, Chi-Wang; Chai, Pao-Hsuan; Chang, Yu-Min

    2007-04-01

    Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO(4)(2-)) to trivalent chromium (Cr(3+)) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1-2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation of Cr(OH)(3(s)) to save the coagulant cost. (3) Higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. For influent chromate concentration of 418 mg/L as Cr(6+), pH 2 and ZVI dosage of 3g (41 g/L), chromate removal was only 29% with hydraulic detention time (HRT) of 1.2 min, but was increased to 99.9% by either increasing HRT to 5.6 min or adjusting pH to 1.5. For iron species at pH 2 and HRT of 1.2 min, Fe(3+) was more thermodynamically stable since oxidizing agent chromate was present. However, if pH was adjusted to 1.5 or 1, where chromate was completely removed, high Fe(2+) but very low Fe(3+) was present. It can be explained that ZVI reacted with chromate to produce Fe(2+) first and the presence of chromate would keep converting Fe(2+) to Fe(3+). Therefore, Fe(2+) is an indicator for complete reduction from Cr(VI) to Cr(III). X-ray diffraction (XRD) was conducted to exam the remained species at pH 2. ZVI, iron oxide and iron sulfide were observed, indicating the formation of iron oxide or iron sulfide could stop the chromate reduction reaction. PMID:16987595

  3. Oxidation of Orange G by persulfate activated by Fe(II), Fe(III) and zero valent iron (ZVI).

    PubMed

    Rodriguez, S; Vasquez, L; Costa, D; Romero, A; Santos, A

    2014-04-01

    Persulfate (PS) was employed in the oxidation of Orange G (OG), an azo dye commonly found in textile wastewaters. Activation of PS was conducted with iron to generate sulfate free radicals (SO4(-)) with high redox potential capable to oxidize most of the organics in water. Identification of oxidation intermediates was carried out by analyzing at different times organic by-products generated from treatment of a concentrate dye solution (11.6 mM) with 153 mM of PS and 20 mM of Fe(II) at 20 °C. Intermediate reaction products (mainly phenol (PH) and benzoquinone (BQ), and in less extent aniline, phenolic compounds and naphthalene type compounds with quinone groups) were identified by GC/MS and HPLC, and an oxidation pathway was proposed for the oxidation of OG with iron activated PS. The effect of iron valence (0, II and III) in the oxidation of an aqueous solution of OG (containing 0.1 mM) was studied in a 0.5 L batch reactor at 20 °C. Initial activator and PS concentrations employed were both 1 mM. Complete pollutant removal was achieved within the first 30 min when iron II or III were employed as activators. Quinone intermediates generated during pollutant oxidation may act as electron shuttles, allowing the reduction of Fe(III) into Fe(II) in the redox cycling of iron. Therefore, activation of PS by Fe(III) allowed complete OG removal. When zero valent iron (ZVI) was employed (particle diameter size 0.74 mm) the limiting step in SO4(-) generation was the surface reaction between ZVI and the oxidant yielding a lower oxidation rate of the dye. An increase in the oxidant dosage (0.2 mM OG, 2 mM Fe(III) and 6 mM PS) allowed complete pollutant and ecotoxicity removal, as well as mineralization close to 75%. PMID:24439838

  4. Remediation of chromate-contaminated groundwater using zero-valent iron: Field test at USCG Support Center, Elizabeth City, North Carolina

    SciTech Connect

    Puls, R.W.; Paul, C.J.; Powell, R.M.

    1996-12-31

    A field test was conducted near an old hard-chrome plating facility on the USCG Support Center near Elizabeth City, North Carolina to evaluate the in situ remediation of ground water contaminated by hexavalent chromium using a passive permeable reactive barrier composed of a zero-valent iron-sand-aquifer material mixture. The remedial effectiveness of this innovative in situ technology was in situ technology was monitored over a one year period.

  5. Nanosilver and Nano Zero-Valent Iron Exposure Affects Nutrient Exchange Across the Sediment-Water Interface.

    PubMed

    Buchkowski, Robert W; Williams, Clayton J; Kelly, Joel; Veinot, Jonathan G C; Xenopoulos, Marguerite A

    2016-01-01

    To examine how nanoparticles influence biogeochemical cycles in streams, we studied the acute impact of nanosilver (nAg) and nanoparticulate zero-valent iron (nZVI) exposure on nutrient and oxygen exchange across the sediment-water interface of two streams (agricultural canal and wetland) that differed in their water quality and sediment characteristics. At the agricultural site, nAg increased oxygen consumption and decreased N2 flux rates from that observed in control incubations. nZVI caused sediment-water systems from both streams to go hypoxic within 1.5 h of exposure. N2 flux rates were at least an order of magnitude higher in nZVI treatments as compared to control. Water column nitrate and nitrite concentrations were not impacted by nZVI exposure but total dissolved phosphorus concentrations were higher in cores treated with nZVI. nAg and nZVI exposure to surface water ecosystems can disrupt ecological function across the sediment-water interface. PMID:26611367

  6. Remediation and phytotoxicity of decabromodiphenyl ether contaminated soil by zero valent iron nanoparticles immobilized in mesoporous silica microspheres.

    PubMed

    Xie, Yingying; Cheng, Wen; Tsang, Pokeung Eric; Fang, Zhanqiang

    2016-01-15

    Polybrominated diphenyl ethers (PBDEs) are a new class of environmental pollutants which easily accumulated in the soil, especially at e-waste sites. However, knowledge about their phytotoxicity after degradation is not well understood. Nano zero valent iron (nZVI) immobilized in mesoporous silica microspheres covered with FeOOH (SiO2@FeOOH@Fe) synthesized in this study was utilized to remove decabromodiphenyl ether (BDE209) from soil. Results revealed that the removal efficiency of BDE209 can be achieved 78% within 120 h using a dosage of 0.165 g g(-1) and a pH of 5.42. Furthermore, the removal efficiency enhanced with increasing soil moisture content and the decreasing of initial BDE209 concentration. Phytotoxicity assays (biomass and germination rate, shoots and roots elongation of Chinese cabbage) were carried out to provide a preliminary risk assessment of treated soil for the application of SiO2@FeOOH@Fe. PMID:26560640

  7. Microbial and mineral evolution in zero valent iron-based permeable reactive barriers during long-term operations.

    PubMed

    Kumar, Naresh; Millot, Romain; Battaglia-Brunet, Fabienne; Omoregie, Enoma; Chaurand, Perrine; Borschneck, Daniel; Bastiaens, Leen; Rose, Jérôme

    2016-03-01

    Impacts of subsurface biogeochemical processes over time have always been a concern for the long-term performance of zero valent iron (Fe(0))-based permeable reactive barriers (PRBs). To evaluate the biogeochemical impacts, laboratory experiments were performed using flow-through glass columns for 210 days at controlled temperature (20 °C). Two different particle sizes of Fe(0) were used in the columns, and to simulate indigenous microbial activity, extra carbon source was provided in the two columns (biotic columns) and the remaining two columns were kept abiotic using gamma radiations. Heavy metals (Zn, As) were removed efficiently in all the columns, and no exhaustion of treatment capability or clogging was observed during our experimental duration. Newly formed Fe mineral phases and precipitates were characterized using X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), and micro-XRF techniques in solid phase at the end of the experiment. In addition, 16S rRNA gene extraction was used for microbial community identification in biotic columns. During the incubation, microbial population shifted in favor of Desulfosporosinus species (sulfate-reducing bacteria) from initial dominance of Acidithiobacillus ferrooxidans in sediments. Dominant mineral phases detected in biotic columns were mackinawite (FeS) and sulfate green rust, while in abiotic columns, magnetite/maghemite phases were more prevalent. PMID:26604198

  8. An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation.

    PubMed

    Zhao, Xiao; Liu, Wen; Cai, Zhengqing; Han, Bing; Qian, Tianwei; Zhao, Dongye

    2016-09-01

    Nano-scale zero-valent iron (nZVI) is one of the most intensively studied materials for environmental cleanup uses over the past 20 years or so. Freshly prepared nZVI is highly reactive due to its high specific surface area and strong reducing power. Over years, the classic borohydride reduction method for preparing nZVI has been modified by use of various stabilizers or surface modifiers to acquire more stable and soil deliverable nZVI for treatment of different organic and inorganic contaminants in water and soil. While most studies have been focused on testing nZVI for water treatment, the greater potential or advantage of nZVI appears to be for in situ remediation of contaminated soil and groundwater by directly delivering stabilized nZVI into the contaminated subsurface as it was proposed from the beginning. Compared to conventional remediation practices, the in situ remediation technique using stabilized nZVI offers some unique advantages. This work provides an update on the latest development of stabilized nZVI for various environmental cleanup uses, and overviews the evolution and environmental applications of stabilized nZVI. Commonly used stabilizers are compared and the stabilizing mechanisms are discussed. The effectiveness and constraints of the nZVI-based in situ remediation technology are summarized. This review also reveals some critical knowledge gaps and research needs, such as interactions between delivered nZVI and the local biogeochemical conditions. PMID:27206054

  9. Decolourization of direct blue 15 by Fenton/ultrasonic process using a zero-valent iron aggregate catalyst.

    PubMed

    Weng, Chih-Huang; Lin, Yao-Tung; Chang, Cheng-Kuan; Liu, Na

    2013-05-01

    Decolourization of direct azo dye, direct blue 15 (DB15), by an advanced Fenton process coupled with ultrasonic irradiation (Fenton/US) was investigated. Zero-valent iron (ZVI) aggregates were used as the catalyst. A positive synergistic effect occurred when Fenton's reagent was combined with ultrasonic irradiation. Experimental results showed that the optimum conditions for decolourization were pH 3.0, Fe(0) 1g/L, H(2)O(2) 5.15×10(-3)mol/L with ultrasound density of 120W/L at 60kHz. These conditions yielded 99% decolouration of 4.7×10(-5) M DB15 (4130 ADMI) solution within 10min. DB15 decolouration follows the first-order decolouration kinetics. Although the solutions containing H(2)CO(3), Cl(-), ClO(4)(-), NO(3)(-) and SO(4)(2-) ions did not have a significant effect on the decolouration, the H(2)PO(4)(-) ion did decrease the decolouration rate. High ultrasonic input power accelerated the reaction and increased decolourization efficiency. The cost effectiveness of this process at high ultrasound density could be controlled despite the high electricity costs incurred by the process. ZVI aggregates were reusable; however, an increase in the number of times ZVI was recycled decreased the decolourization rate. This study demonstrates that a Fenton/US process can effectively decolour the direct azo dye DB15 in wastewater. PMID:23187066

  10. Complete debromination of decabromodiphenyl ether using the integration of Dehalococcoides sp. strain CBDB1 and zero-valent iron.

    PubMed

    Xu, Guiying; Wang, Jiangbo; Lu, Mang

    2014-12-01

    This study investigated the effects of nano- and micro-scale zero-valent iron (nZVI and mZVI) particles on Dehalococcoides sp. strain CBDB1 participating in anaerobic reduction of polybrominated diphenyl ethers. nZVI (>0.25 g L(-)(1)) had an inhibitory effect upon this strain, whereas 1.0 g L(-1) mZVI showed no negative impact on bacterial growth. Strain CBDB1 could only utilize lower brominated congeners (<7 bromines) as electron acceptor. In the bio-ZVI system, decabromodiphenyl ether (BDE-209) was first reduced by ZVI to lower brominated congeners, which were then dehalogenated to diphenyl ether by CBDB1. Within 30 d, a BDE-209 debromination efficiency of 16% and 24% was obtained in the bio-nZVI (0.25 g L(-1)) and bio-mZVI (1.0 g L(-1)) systems with a corresponding diphenyl ether yield efficiency of 14% and 19%, respectively. The debromination efficiency increased significantly from 8% to 24% with an increase of mZVI dosage from 0.25 to 1.0 g L(-1) in the bio-mZVI system. PMID:25217713

  11. Chromate removal by surface-modified nanoscale zero-valent iron: Effect of different surface coatings and water chemistry.

    PubMed

    Dong, Haoran; He, Qi; Zeng, Guangming; Tang, Lin; Zhang, Chang; Xie, Yankai; Zeng, Yalan; Zhao, Feng; Wu, Yanan

    2016-06-01

    This study investigated the correlation between the colloidal stability and reactivity of surface-modified nano zero-valent iron (SM-nZVI) as affected by the surface coating (i.e., polyacrylic acid [PAA] and starch) under various geochemical conditions. Generally, the colloidal stability of nZVI was enhanced with increasing loading of surface coating, while there is an optimum loading for the most efficient Cr(VI) removal by SM-nZVI. At lower loadings than the optimum loading, the surface coating could enhance the particle stabilization, facilitating the Cr(VI) reduction by providing more available surface sites. However, the over-loaded surface coating on the surface of nZVI particles decreased the Cr(VI) reduction due to the occupation of the reactive sites and the inhibition of the mass transfer of Cr(VI) ions from water to the particle surface by providing the electrostatic or steric repulsion. The effects of Ca(2+) ions or humic acid (HA) on the colloidal stability and reactivity of PAA-modified nZVI (P-nZVI) and starch-modified nZVI (S-nZVI) were examined. Differing stability behavior and reactivity were observed for different SM-nZVI. It was found that the presence of Ca(2+) or HA altered surface chemistry of SM-nZVI, the particle-particle interaction and the particle-contaminant interaction, and hence influencing the stability behavior and reactivity of the particles. PMID:26970032

  12. Inhibition or promotion of biodegradation of nitrate by Paracoccus sp. in the presence of nanoscale zero-valent iron.

    PubMed

    Jiang, Chenghong; Xu, Xuping; Megharaj, Mallavarapu; Naidu, Ravendra; Chen, Zuliang

    2015-10-15

    To investigate the effect of nanoscale zero-valent iron (nZVI) on the growth of Paracoccus sp. strain and biodenitrification under aerobic conditions, specific factors were studied, pH, concentration of nitrate, Fe (II) and carbon dioxide. Low concentration of nZVI (50mg/L) promoted both cell growth and biodegradation of nitrate which rose from 69.91% to 76.16%, while nitrate removal fell to 67.10% in the presence of high nZVI concentration (1000 mg/L). This may be attributed to the ions produced in nZVI corrosion being used as an electron source for the biodegradation of nitrate. However, the excess uptake of Fe (II) causes oxidative damage to the cells. To confirm this, nitrate was completely removed after 20 h when 100mg/L Fe (II) was added to the solution, which is much faster than the control (86.05%, without adding Fe (II)). However, nitrate removal reached only 45.64% after 20 h, with low cell density (OD 600=0.62) in the presence of 300 mg/L Fe (II). Characterization techniques indicated that nZVI adhered to microorganism cell membranes. These findings confirmed that nZVI could affect the activity of the strain and consequently change the biodenitrification. PMID:26047857

  13. Tunable synthesis of SiO2-encapsulated zero-valent iron nanoparticles for degradation of organic dyes

    PubMed Central

    2014-01-01

    A series of nanocomposites consisting of zero-valent iron nanoparticles (ZVI NPs) encapsulated in SiO2 microspheres were successfully synthesized through a successive two-step method, i.e., the wet chemical reduction by borohydride followed by a modified Stöber method. The as-synthesized nanocomposites were characterized using X-ray diffraction, field emission scanning electron microscopy, vibrating sample magnetometer, and inductively coupled plasma-atomic emission spectrometer. The catalytic performance of SiO2-encapsulated ZVI nanocomposites for the degradation of organic dyes was investigated using methylene blue (MB) as the model dye in the presence of H2O2. The results showed that the degradation efficiency and apparent rate constant of the degradation reaction were significantly enhanced with increased ZVI NPs encapsulated in SiO2 microspheres, whereas the dosage of H2O2 remarkably promoted degradation rate without affecting degradation efficiency. The content-dependent magnetic property ensured the excellent magnetic separation of degradation products under an external magnet. This strategy for the synthesis of SiO2-encapsulated ZVI NPs nanocomposites was low cost and easy to scale-up for industrial production, thereby enabling promising applications in environmental remediation. PMID:25258615

  14. 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

  15. 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.

  16. Reductive removal of 2,4-dinitrotoluene and 2,4-dichlorophenol with zero-valent iron-included biochar.

    PubMed

    Oh, Seok-Young; Seo, Yong-Deuk; Ryu, Kwang-Sun

    2016-09-01

    In order to remediate organic contaminants in natural waters and soils, a novel zero-valent iron [Fe(0)]-included biochar was synthesized via slow pyrolysis. 2,4-Dinitrotoluene (DNT) and 2,4-dichlorophenol (DCP) were removed in water via sorption to the Fe(0)-included biochar. Compared to sorption control without Fe(0), the sorbed DNT and DCP were further transformed to reduction products by Fe(0)-included biochar. Compared to the reduction control with Fe(0), the presence of biochar promoted the reductive transformation of DNT and DCP. Increasing the pyrolysis temperature resulted in enhancing the removal of DNT and DCP, suggesting that the aromaticity of biochar may be responsible for the removal. The yields of the reduction products also indicated that unlike the direct reduction by Fe(0), different reduction pathways existed in the reduction of DNT and DCP with Fe(0)-included biochar. The results suggest that Fe(0)-included biochar is a viable option to immobilize and transform redox-sensitive organic contaminants in natural environments. PMID:27343454

  17. Nanoscaled zero valent iron/graphene composite as an efficient adsorbent for Co(II) removal from aqueous solution.

    PubMed

    Xing, Min; Wang, Jianlong

    2016-07-15

    A magnetic graphene, i.e., nanoscaled zero valent iron/graphene (0FG) composite, was prepared, characterized and applied for the removal of Co(II) from aqueous solution. The magnetic graphene (0FG) was synthesized through reduction of graphene oxide (GO) and ferrous ions by potassium borohydride. The kinetics and isotherms of Co(II) adsorption onto 0FG were investigated. The mechanism for Co(II) removal was proposed based on the Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and the X-ray absorption fine structure (XAFS) analysis. The results showed that pseudo second-order models and the Freundlich isotherm model fitted well with the data obtained. The adsorption capacity of 0FG was calculated from the Langmuir isotherm, which was 65.58, 101.60 and 134.27mg/g at 10, 20 and 30°C, respectively. Thermodynamic parameters suggested that the adsorption process was endothermic and spontaneous. Co(2+) was stabilized by γ-FeOOH/γ-Fe2O3/Fe3O4 on the surface of graphene sheets, forming CoFe2O4-like nanocrystals. The coordination numbers and interatomic distances indicated that Co(2+) mainly occupied the octahedral site, while pseudo-tetrahedral coordination may occur by dehydroxylation of Co(O,OH)6. Magnetic graphene is a potential adsorbent for Co(2+) removal. PMID:27115333

  18. Simulation of antimony adsorption on nano-zero valent iron and kaolinite and analyzing the influencing parameters.

    PubMed

    Saeidnia, Setareh; Asadollahfardi, Gholamreza; Darban, Ahmad Khodadadi; Mohseni, Mehdi

    2016-01-01

    Antimony is one of the most toxic pollutants in industrial and mineral wastewaters threatening the life of humans and other creatures. We simulated the adsorption of antimony in the presence of nano-zero valent iron (nZVI) adsorbent, on kaolinite and in the presence of nZVI coated on kaolinite from mineral wastewater using VISUAL MINTEQ 3.1 software. Our aim was to determine the factors affecting the adsorption of antimony by applying simulation. The simulation was performed using an adsorption model of a diffuse layer model. The results of the simulation indicated that the nZVI concentration, initial concentrations of antimony and pH factor are effective on the adsorption of antimony. In the conducted stimulation, the optimum pH was 2-5 and the highest adsorption occurred in an acidic state. With increasing initial concentrations of antimony in the simulation, we concluded that nZVI had absorbed various concentrations above 90% and, by increasing the concentration of nZVI, antimony adsorption rate increased. The increased surface area of nZVI and the expansion of more interchangeable surfaces available for reaction with antimony ions causes more antimony ions to be adsorbed. In all cases, the coefficient of determination between the laboratory results and the model predictions that was obtained was more than 0.9. PMID:27191572

  19. Kinetics of Solvent Blue and Reactive Yellow removal using microwave radiation in combination with nanoscale zero-valent iron.

    PubMed

    Mao, Yanpeng; Xi, Zhenqian; Wang, Wenlong; Ma, Chunyuan; Yue, Qinyan

    2015-04-01

    We investigated the efficiency and kinetics of the degradation of soluble dyes over the pH range 5.0-9.0 using a method employing microwave radiation in combination with nanoscale zero-valent iron (MW-nZVI). The nZVI particles (40-70 nm in diameter) were prepared by a liquid-phase chemical reduction method employing starch as a dispersant. Compared to the removal of Solvent Blue 36 and Reactive Yellow K-RN using only nZVI, more rapid and efficient dye removal and total organic carbon removal were achieved using MW-nZVI. The dye removal efficiency increased significantly with decreasing pH, but was negligibly affected by variation in the microwave power. The kinetics of dye removal by MW-nZVI followed both an empirical equation and the pseudo first-order model, while the kinetics of dye removal using nZVI could only be described by an empirical equation. It was also concluded that microwave heating of the dye solutions as well as acceleration of corrosion of nZVI and consumption of Fe(II) were possible reasons behind the enhanced dye degradation. PMID:25872723

  20. Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants.

    PubMed

    Kumar, Naresh; Millot, Romain; Battaglia-Brunet, Fabienne; Négrel, Philippe; Diels, Ludo; Rose, Jérôme; Bastiaens, Leen

    2013-01-01

    In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20±1°C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ(34)S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ(34)S and δ(18)O in biotic conditions and we also highlight a good relationship between δ(34)S and sulfate reduction rate in biotic columns. PMID:23000047

  1. 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. PMID:26998799

  2. Oxalate-assisted oxidative degradation of 4-chlorophenol in a bimetallic, zero-valent iron-aluminum/air/water system.

    PubMed

    Fan, Jinhong; Wang, Hongwu; Ma, Luming

    2016-08-01

    The reaction of zero-valent iron and aluminum with oxygen produced reactive oxidants that can oxidize 4-chlorophenol (4-CP). However, oxidant yield without metal surface cleaning to dissolve the native oxide layer or in the absence of ligands was too low for practical applications. The addition of oxalate (ox) to dissolved oxygen-saturated solution of Fe(0)-Al(0) significantly increased oxidant yield because of the dissolution, pH buffer, and complexing characteristics of ox. Ox-enhanced reactive oxidant generation was affected by ox concentration and solution pH. The critical effect of ox dosing was confirmed with the reactive species of [Fe(II)(ox)0] and [Fe(II)(ox)2 (2-)]. Systematic studies on the effect of the initial and in situ solution pH revealed that 4-CP oxidation was controlled by the continuous release of dissolved Fe(2+) and Al(3+), their fate, and the activation mechanisms of O2 reduction. The degradation pathway of 4-CP in ox-enhanced Fe(0)-Al(0)/O2 may follow the 4-chlorocatechol pathway. The robustness of the ox-enhanced Al(0)-Fe(0)-O2 process was determined with one-time dosing of ox. Therefore, ox is an ideal additive to enhancing the Fe(0)-Al(0)/O2 system for the oxidative degradation of aqueous organic pollutants. PMID:27180839

  3. Targeted removal of trichlorophenol in water by oleic acid-coated nanoscale palladium/zero-valent iron alginate beads.

    PubMed

    Chang, Jaewon; Woo, Heesoo; Ko, Myoung-Soo; Lee, Jaesang; Lee, Seockheon; Yun, Seong-Taek; Lee, Seunghak

    2015-08-15

    A new material was developed and evaluated for the targeted removal of trichlorophenol (TCP) from among potential interferents which are known to degrade removal activity. To achieve TCP-targeted activity, an alginate bead containing nanoscale palladium/zero-valent iron (Pd/nZVI) was coated with a highly hydrophobic oleic acid layer. The new material (Pd/nZVI-A-O) preferentially sorbed TCP from a mixture of chlorinated phenols into the oleic acid cover layer and subsequently dechlorinated it to phenol. The removal efficacy of TCP by Pd/nZVI-A-O was not affected by co-existing organic substances such as Suwannee River humic acid (SRHA), whereas the material without the oleic acid layer (Pd/nZVI-A) became less effective with increasing SRHA concentration. The inorganic substances nitrate and phosphate significantly reduced the reactivity of Pd/nZVI-A, however, Pd/nZVI-A-O showed similar TCP removal efficacies regardless of the initial inorganic ion concentrations. The influence of bicarbonate on the TCP removal efficacies of both Pd/nZVI-A and Pd/nZVI-A-O was not significant. The findings from this study suggest that Pd/nZVI-A-O, with its targeted, constant reactivity for TCP, would be effective for treating this contaminant in surface water or groundwater containing various competitive substrates. PMID:25819991

  4. 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

    2015-01-01

    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 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. PMID:26355955

  5. Functional chitosan-stabilized nanoscale zero-valent iron used to remove acid fuchsine with the assistance of ultrasound.

    PubMed

    Jin, Xiaoying; Zhuang, Zechao; Yu, Bing; Chen, Zhengxian; Chen, Zuliang

    2016-01-20

    Chitosan-stabilized nanoscale zero-valent iron (CS-nZVI) was prepared and used for the removal of acid fuchsine (AF) from aqueous solution with the assistance of ultrasound. More than 98.9% of AF was removed using CS-nZVI, aged CS-nZVI (exposed to air for 2 months), while only 14.6% removal efficiency was achieved after 15 min by chitosan alone with the assistance of ultrasound. Scanning electron microscopy (SEM) confirmed that chitosan polymers were arranged in a homocentric layered structure. Thus, the polymer can prevent the aggregation of nZVI and increase their anti-oxidation capacity. X-ray diffraction (XRD) also suggested that the chitosan used in synthesis may protect nZVI nanoparticles from air oxidation. Different factors impacting on the removal of AF using CS-nZVI showed that the reduction increased when dosage and temperature increased, but decreased when pH and initial concentration rose. Kinetic studies revealed that the removal of AF fitted well to the pseudo-first-order model. The apparent activation energy was 55.34 kJ/mol, indicating a chemically controlled reaction. Finally, the application of CS-nZVI in dyeing wastewater led to a removal efficiency of 99% of AF, while the reuse test confirmed that AF's removal efficiency declined from 99.6 to 39.3% after seven cycles. PMID:26572450

  6. Electromagnetic Borehole Flowmeter Surveys at Selected In Situ Redox Manipulation Barrier Wells, Zero-Valent Iron Site, Hanford, Washington

    SciTech Connect

    Newcomer, Darrell R.

    2009-02-09

    Ambient (i.e., static) and dynamic (i.e., pumping-induced) electromagnetic borehole flowmeter (EBF) surveys were performed in 10 selected In Situ Redox Manipulation (ISRM) barrier wells to characterize the distribution of in-well vertical flow conditions and to infer the relative hydraulic conductivity distribution in the upper-part of the unconfined aquifer. These wells are located in two areas where the aquifer is targeted for testing of zero-valent iron injection to mend a failed portion of the ISRM barrier at the 100 D Area, Hanford Site. Each of these two areas consists of a group of five wells, one group to the southwest and one group to the northeast. The upper ~15 to 20 ft (~4.6 to 6.1 m) of the unconfined aquifer was characterized for in-well vertical flow conditions and vertical profile information regarding relative hydraulic conductivity. At some well site locations, the upper ~2 to 3 ft (~0.6 to 1 m) of the well-screen interval could not be characterized under pumping (dynamic) conditions because of the presence of the pump.

  7. Synthesis and characterization of porous zero-valent iron nanoparticles for remediation of chromium-contaminated wastewater.

    PubMed

    Lin, Kuen-Song; Dehvari, Khalilalrahman; Liu, Yeu-Jye; Kuo, Hua; Hsu, Pei-Ju

    2013-04-01

    The physical and chemical properties of porous zero-valent iron nanoparticles (ZVINs) have highly been acknowledged in the decontamination of heavy metal containing wastes and groundwater. In the present work, the treatment of Cr-contaminant through adsorption onto the ZVINs has been studied. The morphology, crystal structure, and surface composition of Fe(O) nanoparticles were investigated by field emission scanning electron microscopy/energy dispersive X-ray spectroscopy (FE-SEM/EDS), transmission electron microscope (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. X-ray absorption near edge structure (XANES) revealed that the Cr(VI) species reduce to Cr(III) while oxidizing the ZVINs to Fe2O3, Fe3O4 or FeO electrochemically. Furthermore, the nitrogen adsorption-desorption isotherm of the porous nanoparticles was similar to a type IV curve with an obvious mesopore-characteristic H3 hysteresis loop, whereas the sizes of mesopores were in the range of 30-50 nm. Experimentally, the efficiency for Cr(VI) removal in the range of 150-300 ppm was found to be > 99.9%. Remarkably, the reduction reaction was completed within 10 min in the absence of additional pH controls. This work also highlights the utility of X-ray absorption spectroscopy (XAS) coupled with conventional characterization methods to comprehensively study the speciation and possible reaction pathway in adsorption process. PMID:23763143

  8. Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron.

    PubMed

    Cao, Menghua; Wang, Linling; Wang, Li; Chen, Jing; Lu, Xiaohua

    2013-02-01

    Application of a novel Fenton-like system with zero-valent iron, EDTA and Air (ZVI/EDTA/Air) was investigated to degrade dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene (DDE) in the actual contaminated soil from an organochlorine pesticide site. It was found DDTs in the soil were effectively degraded by the system at room temperature, ambient atmosphere pressure and near neutral pH. The dosages of EDTA and ZVI were the dominant factors influencing the removal of contaminants. An increase of EDTA from 0.05 to 0.2 mM and ZVI from 1 to 5 g L(-1) improved the removal of the contaminants significantly. However, excessive amount of EDTA led to a negative effect on the degradation process. Meanwhile, EDTA was simultaneously degraded so as to avoid the secondary pollution risk on soil remediation. Only a small amount of 4,4'-DDE and 2,2-bis(4-chlorophenyl)-1-chloroethylene (4,4'-DDMU) generated as the intermediates of DDT degradation during the process. Our investigation suggests that the Fenton-like system is a promising alternative for remediation of organochlorine pesticides contaminated soils. PMID:23102698

  9. Role of oxidative stress in inactivation of Escherichia coli BW25113 by nanoscale zero-valent iron.

    PubMed

    Chaithawiwat, Krittanut; Vangnai, Alisa; McEvoy, John M; Pruess, Birgit; Krajangpan, Sita; Khan, Eakalak

    2016-09-15

    An Escherichia coli BW25113 wildtype strain and mutant strains lacking genes that protect against oxidative stress were examined at different growth phases for susceptibility to zero-valent iron (nZVI). Viability of cells was determined by the plate count method. All mutant strains were more susceptible than the wild type strain to nZVI; however, susceptibility differed among the mutant strains. Consistent with the role of rpoS as a global stress regulator, an rpoS gene knockout mutant exhibited the greatest susceptibility to nZVI under the majority of conditions tested (except exponential and declining phases at longer exposure time). Mutants lacking genes encoding the inducible and constitutively expressed cytosolic superoxide dismutases, sodA and sodB, respectively, were more susceptible to nZVI than a mutant lacking the gene encoding sodC, a periplasmic superoxide dismutase. This suggests that nZVI induces oxidative stress inside the cells via superoxide generation. Quantitative polymerase chain reaction was used to examine the expression of katG, a gene encoding the catalase-peroxidase enzyme, in nZVI-treated E. coli at different growth phases. Results showed that nZVI repressed the expression of katG in all but lag phases. PMID:26953142

  10. Nonionic surfactant greatly enhances the reductive debromination of polybrominated diphenyl ethers by nanoscale zero-valent iron: mechanism and kinetics.

    PubMed

    Liang, Da-wei; Yang, Yu-han; Xu, Wei-wei; Peng, Si-kan; Lu, Shan-fu; Xiang, Yan

    2014-08-15

    Nanoscale zero-valent iron (nZVI) has been considered as an effective agent for reductive debromination of polybrominated diphenyl ethers (PBDEs). But the high lipophilicity of PBDEs will hinder their debromination owing to the inefficient contact of PBDEs with nZVI. In this study, different ionic forms of surfactants were investigated aiming to promote PBDE debromination, and the beneficial effects of surfactant were found to be: nonionic polyethylene glycol octylphenol ether (Triton X-100, TX)>cationic cetylpyridinium chloride (CPC)>anionic sodium dodecyl benzenesulfonate (SDDBS). Except for with SDDBS, the promotion effect for PBDE debromination was positively related to the surfactant concentrations until a critical micelle concentration (CMC). The debromination process of octa-BDE and its intermediates could be described as a consecutive reaction. The corresponding rate constants (k) for the debromination of parent octa-BDE (including nona- to hepta-BDEs), the intermediates hexa-, penta-, and tetra-BDEs are 1.24 × 10(-1) h(-1), 8.97 × 10(-2) h(-1), 6.50 × 10(-2) h(-1) and 2.37 × 10(-3) h(-1), respectively. PMID:25019577

  11. The role of magnetite nanoparticles in the reduction of nitrate in groundwater by zero-valent iron.

    PubMed

    Cho, Dong-Wan; Song, Hocheol; Schwartz, Franklin W; Kim, Bokseong; Jeon, Byong-Hun

    2015-04-01

    Magnetite nanoparticles were used as an additive material in a zero-valent iron (Fe0) reaction to reduce nitrate in groundwater and its effects on nitrate removal were investigated. The addition of nano-sized magnetite (NMT) to Fe0 reactor markedly increased nitrate reduction, with the rate proportionally increasing with NMT loading. Field emission scanning electron microscopy analysis revealed that NMT aggregates were evenly distributed and attached on the Fe0 surface due to their magnetic properties. The rate enhancement effect of NMT is presumed to arise from its role as a corrosion promoter for Fe0 corrosion as well as an electron mediator that facilitated electron transport from Fe0 to adsorbed nitrate. Nitrate reduction by Fe0 in the presence of NMT proceeded much faster in groundwater (GW) than in de-ionized water. The enhanced reduction of nitrate in GW was attributed to the adsorption or formation of surface complex by the cationic components in GW, i.e., Ca2+ and Mg2+, in the Fe0-H2O interface that promoted electrostatic attraction of nitrate to the reaction sites. Moreover, the addition of NMT imparted superior longevity to Fe0, enabling completion of four nitrate reduction cycles, which otherwise would have been inactivated during the first cycle without an addition of NMT. The results demonstrate the potential applicability of a Fe0/NMT system in the treatment of nitrate-contaminated GW. PMID:25665757

  12. Investigation of the long-term performance of zero-valent iron for reductive dechlorination of trichloroethylene

    SciTech Connect

    Farrell, J.; Kason, M.; Melitas, N.; Li, T.

    2000-02-01

    This research investigated the long-term performance of zero-valent iron for mediating the reductive dechlorination of trichloroethylene (TCE). Over a 2-year period, rates of TCE dechlorination in columns packed with iron filings were measured in simulated groundwaters containing either 3 mM CaSO{sub 4}, 5 mM CaCl{sub 2}, or 5 mM Ca(NO{sub 3}){sub 2}. At early elapsed times, TCE reaction rates were pseudo-first-order in TCE concentration and were independent of the solution pH. With increasing elapsed time, reaction rates deviated from pseudo-first-order behavior due to reactive site saturation and increased iron surface passivation toward the influent end of each column. The extent of passivation was dependent on both the TCE concentration and the background electrolyte solution. For most of the investigation, TCE reaction rates in 3 mM CaSO{sub 4} and 5 mM CaCl{sub 2} solutions were statistically identical at the 0.05 confidence level. However, TCE reaction rates in 5 mM Ca(NO{sub 3}){sub 2} were slower. In columns operated using chloride- and sulfate-containing waters, the effective half-life for TCE dechlorination increased from approximately 400 min after 10 days elapsed to approximately 2,500 min after 667 days. The effective TCE half-life in the nitrate-containing water increased from approximately 1,500 min after 10 days to approximately 3,500 min after 667 days. Measurements of iron corrosion rates in nitrate and chloride solutions showed that nitrate contributed to increased iron surface passivation and decreased rates of iron corrosion. Corrosion current measurements indicated that halocarbon reduction on fresh iron surfaces was cathodically controlled, whereas on aged iron surfaces, iron corrosion was anodically controlled. Anodic control of iron corrosion contributed to the development of reactive site saturation with time and to similar reaction rates for TCE and perchloroethylene. Passivation of the iron surfaces was found to be dependent on the

  13. Removal of dissolved metals by zero-valent iron (ZVI): kinetics, equilibria, processes and implications for stormwater runoff treatment.

    PubMed

    Rangsivek, R; Jekel, M R

    2005-10-01

    Infiltration of stormwater runoff contaminated with metals is often questionable in several cases due to its long-term potential to cause deterioration of groundwater quality. To ensure the quality of filtrate, a pre-treatment of contaminated runoff is required. This study investigates the processes of copper and zinc ion removal from stormwater runoff using zero-valent iron (ZVI, Fe0). Kinetic and equilibrium tests were performed with laboratory-prepared and in situ stormwater runoff samples collected from roof, street and highway catchments. Based on the results, a substantial portion of Cu2+ is reduced and transformed to insoluble forms of Cu0 and Cu2O. Unlike copper, the adsorption and co-precipitation associated with freshly precipitated iron oxides play important roles for the removal of Zn2+. Investigations under various water quality conditions demonstrated a relatively minor impact on Cu2+ uptake rates. However, the different conditions apparently altered the removal stoichiometry and phases of the copper deposits. The removal rates of Zn2+ increase with higher dissolved oxygen (DO), ionic strength (IS), temperature (T) and pH. Dissolved organic carbon (DOC) in runoff samples forms complexes with metals and Fe2+, thereby kinetically decreasing the metal uptake rates. Furthermore, depending on its composition, a larger molecular weight organic fraction was found to preferentially compete for the adsorption sites. The study demonstrates that ZVI is a promising medium for achieving comparable capacity to a commercial adsorbent like granular ferric hydroxide (GFH). Long-term performance of ZVI, however, may be limited and governed by the formation of non-conductive layers of iron and cuprous oxides. PMID:16181656

  14. Application of zero-valent iron nanoparticles for the removal of aqueous zinc ions under various experimental conditions.

    PubMed

    Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2014-01-01

    Application of zero-valent iron nanoparticles (nZVI) for Zn²⁺ removal and its mechanism were discussed. It demonstrated that the uptake of Zn²⁺ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn²⁺ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn²⁺ removal by nZVI. The DO enhanced the removal efficiency of Zn²⁺. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn²⁺ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn²⁺ by nZVI because the existing H⁺ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn²⁺ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn²⁺ were higher than Cd²⁺. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn²⁺. PMID:24416439

  15. Degradation of trinitroglycerin (TNG) using zero-valent iron nanoparticles/nanosilica SBA-15 composite (ZVINs/SBA-15).

    PubMed

    Saad, Rabih; Thiboutot, Sonia; Ampleman, Guy; Dashan, Wang; Hawari, Jalal

    2010-11-01

    Trinitroglycerin (TNG) is an industrial chemical mostly known for its clinical use in treating angina and manufacturing dynamite. The wide manufacture and application of TNG has led to contamination of vast areas of soil and water. The present study describes degradation of TNG with zero-valent iron nanoparticles (ZVINs) in water either present alone or stabilized on nanostructured silica SBA-15 (Santa Barbara Amorphous No. 15). The BET surface areas of ZVINs/SBA-15 (275.1 m2 g(-1)), as determined by nitrogen adsorption-desorption isotherms, was much larger than the non-stabilized ZVINs (82.0 m2 g(-1)). X-ray diffraction (XRD) showed that iron in both ZVINs and ZVINs/SBA-15 was present mostly in the α-Fe0 crystalline form considered responsible for TNG degradation. Transmission Electron Microscopy (TEM) showed that iron nanoparticles were well dispersed on the surface of the nanosilica support. Both ZVINs and ZVINs/SBA-15 degraded TNG (100%) in water to eventually produce glycerol and ammonium. The reaction followed pseudo-first-order kinetics and was faster with ZVINs/SBA-15 (k1 0.83 min(-1)) than with ZVINs (k1 0.228 min(-1)). The corresponding surface-area normalized rate constants, knorm, were 0.36 and 0.33 L h(-1) m(-2) for ZVINs/SBA-15 and ZVINs, respectively. The ZVINs/SBA-15 retained its original degradation efficiency of TNG after repeatedly reacting with fresh nitrate ester for five successive cycles. The rapid and efficient transformation of TNG with ZVINs/SBA-15, combined with excellent sustained reactivity, makes the nanometal an ideal choice for the clean up of water contaminated with TNG. PMID:20801482

  16. 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.

  17. 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. PMID:27105151

  18. The dual effects of carboxymethyl cellulose on the colloidal stability and toxicity of nanoscale zero-valent iron.

    PubMed

    Dong, Haoran; Xie, Yankai; Zeng, Guangming; Tang, Lin; Liang, Jie; He, Qi; Zhao, Feng; Zeng, Yalan; Wu, Yanan

    2016-02-01

    Nanoscale zero-valent iron (NZVI) particles are usually modified with surface coating to mitigate the particle stability in water during the environmental application. However, the surface coating may not only influence the particle stabilization but also the particle cytotoxicity. In this study, we investigated the dual effects of carboxymethyl cellulose (CMC) on the colloidal stability and cytotoxicity of NZVI towards gram-negative Escherichia coli (E. coli) and discussed the interrelation between particle stability and cytotoxicity. The effect of CMC concentration, ionic strength (Ca(2+)) and aging treatment on the particle cytotoxicity were also examined. Specifically, the aqueous stability of NZVI suspensions with CMC ratio dose-dependently strengthened within 1 h. The inactivation of E. coli by bare NZVI was significant and concentration- and time-dependent. On the contrary, an increasing reduction in cytotoxicity of NZVI with CMC ratio increasing was observed, even though the particles became more dispersed. TEM analysis demonstrates the membrane disruption and the cellular internalization of nanoparticles after exposure of E. coli to NZVI. However, in the case of CMC-modified NZVI (CNZVI), the bacterial cell wall displays an outer shell of a layer of nanoparticles attached around the outer membrane, but the cell membrane was kept intact. The presence of Ca(2+) can either increase or decrease the cytotoxicity of NZVI and CNZVI, depending on the concentration. The aged NZVI and CNZVI particles did not seem to present obvious bactericidal effect due to the transformation of Fe(0) to the less toxic or non-toxic iron oxides, as indicated by the XRD analysis. PMID:26519799

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

    PubMed

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

    2015-03-01

    Oxidations of nanoscale zero-valent iron (nZVI) under aerobic (dissolved oxygen≈8mgL(-1)) and anaerobic (dissolved oxygen <3mgL(-1)) conditions were simulated, and their influences on aggregation behaviors of nZVI were investigated. The two oxidation products were noted as HO-nZVI (nZVI oxidized in highly oxygenated water) and LO-nZVI (nZVI oxidized in lowly oxygenated water) respectively. The metallic iron of the oxidized nZVI was almost exhausted (Fe(0)≈8±5%), thus magnetization mainly depended on magnetite content. Since sufficient dissolved oxygen led to the much less magnetite (∼15%) in HO-nZVI than that in LO-nZVI (>90%), HO-nZVI was far less magnetic (Ms=88kAm(-1)) than LO-nZVI (Ms=365kAm(-1)). Consequently, HO-nZVI formed small agglomerates (228±10nm), while LO-nZVI tended to form chain-like aggregations (>1μm) which precipitated rapidly. Based on the EDLVO theory, we suggested that dissolved oxygen level determined aggregation morphologies by controlling the degree of oxidation and the magnitude of magnetization. Then the chain-like alignment of LO-nZVI would promote further aggregation, but the agglomerate morphology of HO-nZVI would eliminate magnetic forces and inhibit the aggregation while HO-nZVI remained magnetic. Our results indicated the fine colloidal stability of HO-nZVI, which might lead to the great mobility in the environment. PMID:25441925

  20. Capture and storage of hydrogen gas by zero-valent iron.

    PubMed

    Reardon, Eric J

    2014-02-01

    Granular Fe(o), used to reductively degrade a variety of contaminants in groundwater, corrodes in water to produce H2(g). A portion enters the Fe(o) lattice where it is stored in trapping sites such as lattice defects and microcracks. The balance is dissolved by the groundwater where it may exsolve as a gas if its solubility is exceeded. Gas exsolution can reduce the effectiveness of the Fe(o) treatment zone by reducing contact of the contaminant with iron surfaces or by diverting groundwater flow. It also represents a lost electron resource that otherwise could be involved in reductive degradation of contaminants. It is advantageous to select an iron for remediation purposes that captures a large proportion of the H2(g) it generates. This study examines various aspects of the H2(g) uptake process and has found 1) H2(g) does not have to be generated at the water/iron interface to enter the lattice. It can enter directly from the gas/water phases, 2) exposure of granular sponge iron to H2(g) reduces the dormant period for the onset of iron corrosion, 3) the large quantities of H2(g) generated by nano-Fe(o) injected into a reactive barrier of an appropriate granular iron can be captured in the lattice of that iron, and 4) lattice-bound hydrogen represents an additional electron resource to Fe(o) for remediation purposes and may be accessible using physical or chemical means. PMID:24389351

  1. Capture and storage of hydrogen gas by zero-valent iron

    NASA Astrophysics Data System (ADS)

    Reardon, Eric J.

    2014-02-01

    Granular Feo, used to reductively degrade a variety of contaminants in groundwater, corrodes in water to produce H2(g). A portion enters the Feo lattice where it is stored in trapping sites such as lattice defects and microcracks. The balance is dissolved by the groundwater where it may exsolve as a gas if its solubility is exceeded. Gas exsolution can reduce the effectiveness of the Feo treatment zone by reducing contact of the contaminant with iron surfaces or by diverting groundwater flow. It also represents a lost electron resource that otherwise could be involved in reductive degradation of contaminants. It is advantageous to select an iron for remediation purposes that captures a large proportion of the H2(g) it generates. This study examines various aspects of the H2(g) uptake process and has found 1) H2(g) does not have to be generated at the water/iron interface to enter the lattice. It can enter directly from the gas/water phases, 2) exposure of granular sponge iron to H2(g) reduces the dormant period for the onset of iron corrosion, 3) the large quantities of H2(g) generated by nano-Feo injected into a reactive barrier of an appropriate granular iron can be captured in the lattice of that iron, and 4) lattice-bound hydrogen represents an additional electron resource to Feo for remediation purposes and may be accessible using physical or chemical means.

  2. Interfacial phenomena affecting contaminant remediation with zero-valent iron metal

    SciTech Connect

    Tratnyek, P.G.; Johnson, T.; Schattauer, A.

    1995-12-31

    The purposes of this paper are to discuss the importance of oxygen (or anoxia) in organic contaminant degradation by granular iron metal, and to explore the various ways in which corrosion, precipitation, and mass transport effects on iron reactivity reflect interfacial phenomena. Studies illustrating the importance of zone-scale and grain-scale interfaces are summarized. The effect of O{sub 2} on dechlorination rates is also briefly discussed, along with possible reaction mechanisms.

  3. Polyelectrolyte multilayer-assisted immobilization of zero-valent iron nanoparticles onto polymer nanofibers for potential environmental applications.

    PubMed

    Xiao, Shili; Wu, Siqi; Shen, Mingwu; Guo, Rui; Huang, Qingguo; Wang, Shanyuan; Shi, Xiangyang

    2009-12-01

    We report a facile approach to synthesizing and immobilizing zero-valent iron nanoparticles (ZVI NPs) onto polyelectrolyte (PE) multilayer-assembled electrospun polymer nanofibers for potential environmental applications. In this approach, negatively charged cellulose acetate (CA) nanofibers fabricated by electrospinning were assembled with multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and polyacrylic acid (PAA) through electrostatic layer-by-layer assembly. The formed PAA/PDADMAC multilayers onto CA nanofibers were then used as a nanoreactor to complex Fe(II) ions through the binding with the free carboxyl groups of PAA for subsequent reductive formation of ZVI NPs. Combined scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetry analysis studies demonstrate that the ZVI NPs are successfully synthesized and uniformly distributed into the PE multilayers assembled onto the CA nanofibers. The produced hybrid nanofibrous mats containing ZVI NPs were found to exhibit superior capability to decolorize acid fuchsin, an organic dye in dyeing wastewater. We show that the loading capacity of ZVI NPs can be tuned by changing the number of PE layers and the cycles of binding/reduction process. Increasing the number of the binding/reduction cycles leads to a slight bigger size of the ZVI NPs, which is not beneficial for improving the reactivity of ZVI NPs. The present approach to synthesizing and immobilizing ZVI NPs onto polymer nanofibers opens a new avenue to fabricating various fiber-based composite materials with a high surface area to volume ratio for environmental, catalytic, and sensing applications. PMID:20356166

  4. Transformation of chlorinated hydrocarbons using aquocobalamin or coenzyme F{sub 430} in combination with zero-valent iron

    SciTech Connect

    Morra, M.J.; Borek, V.; Koolpe, J.

    2000-06-01

    More effective methods are necessary for the remediation of soils, sediments, and ground waters contaminated with halogenated organic compounds. The authors objective was to determine the feasibility and utility of using a tetrapyrrole-Fe(0) mixture for reductive dehalogenation of synthetic organic contaminants. Aquocobalamin or coenzyme F{sub 430} was combined with Fe(0) in aqueous systems containing either a single chlorinated compound or mixtures of chlorinated compounds, and substrate disappearance was monitored using gas chromatography-mass spectrometry (GC-MS). Zero-valent iron effectively dehalogenated CCl{sub 4} at low to neutral pH values, while increases in CCl{sub 4} dehalogenation resulting from inclusion of tetrapyrrole catalysts along with Fe(0) occurred only at basic pH values. Rates of CCl{sub 4} disappearance increased with additional aquocobalamin, but reached a maximum and decreased at higher aquocobalamin concentrations. overall dehalogenation rates may thus be a function of Fe(0)'s limited reactive surface area. There was a trend for both tetrapyrrole catalysts to promote the disappearance of halogenated compounds in a mixed substrate containing 20 compounds. Studies with five individual substrates likewise showed trends for increased substrate removal with F{sub 430} beyond that for Fe(0) alone. This increase is most important for compounds such as 1,2-dichloroethane and 1,4-dichlorobenzene that are not readily dehalogenated by Fe(0). Chloride concentrations in the reaction mixtures indicated that reductive dehalogenation was the dominant process responsible for substrate disappearance. Use of a combination of aquocobalamin or coenzyme F{sub 430} and Fe(0) may effectively promote dehalogenation, thus producing fewer products and more complete dehalogenation of the target substrates than can be achieved using only one of the abiotic reductants alone.

  5. High Precision Measurements of 235U/238U Isotopic Fractionations Resulting From Uranium Reduction Induced by Zero Valent Iron

    NASA Astrophysics Data System (ADS)

    Rademacher, L.; Lundstrom, C.; Johnson, T.

    2003-12-01

    Uranium is a widespread natural and anthropogenic contaminant in surface and subsurface waters. Like several other inorganic contaminants, uranium is mobile under oxidizing conditions but may be immobilized by chemical reduction. U(VI) moves with groundwater as (UO2)2+ and as soluble complexes with carbonate, phosphate, and fluoride. In many groundwater systems, uranium undergoes chemical reduction to U(IV), which is insoluble and immobile. Therefore, understanding the extent of reduction is essential for predicting the mobility of uranium in groundwater. Mass dependent isotopic fractionations of redox sensitive contaminants frequently found in groundwater (including chromate, selenate, and nitrate) have proven exceptionally useful for estimating the rate and extent of reduction and immobilization. Until recently, however, analytical limitations have prevented these techniques from being applied to heavier redox sensitive elements, such as uranium. The advent of highly sensitive multi-collector inductively coupled plasma mass spectrometers (MC-ICP-MS) enables high precision measurements of previously undetected variations in many elements. Laboratory reduction experiments with zero valent iron (ZVI) were performed in a controlled environment to test the hypothesis that uranium isotopes, specifically 235U/238U, behave similarly to other redox sensitive contaminants and produce a mass dependent fractionation during the transformation between valence states. Because of the large abundance differences between 235U and 238U, initial experiments used U500, an enriched uranium standard with approximately equal parts 235U and 238U. Results suggest that the highly sensitive MC-ICP-MS distinguishes 235U/238Uvariations to approximately + 0.02per mil. Measured isotopic fractionations between the 235U/238U of the initial and final experimental solutions (~70% reduced) are approximately 1.1 per mil, and increase with decreasing concentration. Measured variations in 235U/238U

  6. Nano-scale zero valent iron transport in a variable aperture dolomite fracture and a glass fracture

    NASA Astrophysics Data System (ADS)

    Mondal, P.; Sleep, B. E.; Cui, Z.; Zhou, Z.

    2014-12-01

    Experiments and numerical simulations are being performed to understand the transport behavior of carboxymethyl cellulose polymer stabilized nano-scale zero valent iron (nZVI) in a variable aperture dolomite rock fracture and a variable aperture glass replica of a fractured slate. The rock fracture was prepared by artificially inducing a fracture in a dolomite block along a stylolite, and the glass fracture was prepared by creating molds with melted glass on two opposing sides of a fractured slate rock block. Both of the fractures were 0.28 m in length and 0.21 m in width. Equivalent hydraulic apertures are about 110 microns for the rock fracture and 250 microns for the glass replica fracture. Sodium bromide and lissamine green B (LGB) serve as conservative tracers in the rock fracture and glass replica fracture, respectively. A dark box set-up with a light source and digital camera is being used to visualize the LGB and CMC-nZVI movement in the glass fracture. Experiments are being performed to determine the effects of water specific discharge and CMC concentration on nZVI transport in the fractures. Transmission electron microscopy, dynamic light scattering, and UV-visual spectrophotometry were performed to determine the stability and characteristics of the CMC-nZVI mixture. The transport of bromide, LGB, CMC, and CMC-nZVI in both fractures is being evaluated through analysis of the effluent concentrations. Time-lapse images are also being captured for the glass fracture. Bromide, LGB, and CMC recoveries have exceeded 95% in both fractures. Significant channeling has been observed in the fractures for CMC transport due to viscous effects.

  7. Simultaneous removal of NO and SO{sub 2} by high-temperature fluidized zero-valent iron processes

    SciTech Connect

    Shiao-Shing Chen; Chih-Yu Cheng; Chung-Cheng Wei; Chao-Heng Tseng

    2007-03-15

    A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO{sub 2}) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO{sub 2}, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm{sub 2} min for temperature 573 K, there is neither NO nor SO{sub 2} reduction. For 623 K and 673 K, complete removal for NO and 90% removal for SO{sub 2} were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO{sub 2}. The amounts of NO or SO{sub 2} reduction increased as temperature increased, and linearities were observed with both correlation coefficients 0.97. Compared with NO, SO{sub 2} had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO{sub 2}. At the same temperature, both NO and SO{sub 2} reductions were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters and assess the breakthrough time of NO and SO{sub 2}. Higher breakthrough time was achieved for higher W/F value. Longer breakthrough time and more NO and SO{sub 2} mass reduction were achieved for combined NO and SO{sub 2} than individual NO or SO{sub 2} treated by ZVI, and both oxidation and reduction reactions occurred. 15 refs., 8 figs., 1 tab.

  8. Particles and enzymes: Combining nanoscale zero valent iron and organochlorine respiring bacteria for the detoxification of chloroethane mixtures.

    PubMed

    Koenig, Joanna C; Boparai, Hardiljeet K; Lee, Matthew J; O'Carroll, Denis M; Barnes, Robert J; Manefield, Michael J

    2016-05-01

    Nanoscale zero valent iron (nZVI) and organochlorine respiring bacteria (ORB) are two technologies used to detoxify chlorinated aliphatic hydrocarbons (CAHs). nZVI can rapidly detoxify high CAH concentrations, but is quickly oxidised and unable to degrade certain CAHs (e.g., 1,2-dichlorothane). In contrast, ORB can dechlorinate CAHs resistant to nZVI (e.g., 1,2-dichlorothane) but are inhibited by other CAHs of concern degradable by nZVI (e.g., chloroform and carbon tetrachloride). Combining the two was proposed as a unique treatment train to overcome each technology's shortcomings. In this study, this combined remedy was investigated using a mixture of 1,2-dichloroethane, degradable by ORB but not nZVI, and 1,1,2-trichloroethane, susceptible to both. Results indicated that nZVI rapidly dechlorinated 1,1,2-trichloroethane when supplied above 0.5 g/L, however ORB were inhibited and unable to dechlorinate 1,2-dichloroethane. pH increase and ionic species associated with nZVI did not significantly impact ORB, pinpointing Fe(0) particles as responsible for ORB inhibition. Below 0.05 g/L nZVI, ORB activity was stimulated. Results suggest that combining ORB and nZVI at appropriate doses can potentially treat a wider range of CAHs than each individual remedy. At field sites where nZVI was applied, it is likely that in situ nZVI concentrations were below the threshold of negative consequences. PMID:26808236

  9. Remediation of TCE-contaminated groundwater using zero valent iron and direct current: experimental results and electron competition model

    NASA Astrophysics Data System (ADS)

    Moon, Ji-Won; Moon, Hi-Soo; Kim, Heonki; Roh, Yul

    2005-09-01

    The objectives of this study are to design an optimal electro-enhanced permeable reactive barrier (E2PRB) system for the remediation of trichloroethylene (TCE)-contaminated water using zero valent iron (ZVI) and direct current (DC) and to investigate the mechanisms responsible for TCE degradation in different ZVI-DC configurations. A series of column experiments was conducted to evaluate the effect of different arrangements of electrodes and ZVI barriers in the column on the TCE removal capacity (RC). In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive dechlorination of TCE was improved up to six times with simultaneous application of ZVI and DC compared to that using ZVI only. The most effective arrangement of electrode and ZVI for TCE removal was the column set with ZVI and a cathode installed at the down gradient. Based on the electrokinetic study for the column systems with only DC input, single acid front movement could explain different RCs. An enhanced dechlorination rate of TCE using E2PRB systems, compared to a conventional PRB system, was observed, and is considered to be attributed to more electron sources: (1) external DC, (2) electrolysis of water, (3) oxidation of ZVI, (4) oxidation of dissolved Fe2+, (5) oxidation of molecular hydrogen at the cathode, and (6) oxidation of Fe2+ in mineral precipitates. Each of these electron sources was evaluated for their potential influencing the TCE RC through the electron competition model and energy consumption. A strong correlation between the quantity of electrons generated, RC, and the energy-effectiveness was found.

  10. Enhanced treatment of wastewater from the vitamin C biosynthesis industry using a UASB reactor supplemented with zero-valent iron.

    PubMed

    Shi, Rongjiu; Xu, Hui; Zhang, Ying

    2011-12-01

    The effects of zero-valent iron (Fe0) on the performance of a mesophilic upflow anaerobic sludge blanket (UASB) reactor treating high-strength wastewater from the vitamin C biosynthesis industry (VCW) was investigated during a 200-day period. The results showed that the chemical oxygen demand (COD) removal efficiency, CH4 content in biogas, specific methanogenic activity of sludge, and phosphate removal efficiency were significantly improved up to 81.8-96.1%, 76.5-79.6%, 1.71-2.87 g CH4-COD g(-1) VSS d(-1) and 68.5-85.2%, respectively, at elevated organic loading rates (OLRs) in the Fe0-amended reactor (RFe). In contrast, the corresponding values of 65.3-83.4%, 69.1-70.8%, 1.12-1.95 g CH4-COD g(-1) VSS d(-1) and 1.4-1.6%, respectively, were recorded in the control (R0). Elevated ferrous concentration of nearly 400 mg L(-1) in sludge was detected in RFe, whereas in the effluent of both reactors it was low (< 1.0 mg L(-1)). Batch tests further showed that Fe0 significantly enhanced the biodegradability of the VCW as shown by an increase in BOD/COD ratio from 0.41 to 0.65, and could serve as the electron donor for methanogenesis by anaerobic sludge, which were responsible for the differences between RFe and R0. The results suggest this integrated Fe0-microbial system is promising in facilitating the anaerobic digestion of VCW in UASB reactors. PMID:22439574

  11. Oxidant production from corrosion of nano- and microparticulate zero-valent iron in the presence of oxygen: a comparative study.

    PubMed

    Lee, Hongshin; Lee, Hye-Jin; Kim, Hyung-Eun; Kweon, Jihyang; Lee, Byeong-Dae; Lee, Changha

    2014-01-30

    In aqueous solution, zero-valent iron (ZVI, Fe(0)) is known to activate oxygen (O2) into reactive oxidants such as hydroxyl radical and ferryl ion capable of oxidizing contaminants. However, little is known about the effect of the particle size of ZVI on the yield of reactive oxidants. In this study, the production of reactive oxidants from nanoparticulate and microparticulate ZVIs (denoted as nZVI and mZVI, respectively) was comparatively investigated in the presence of O2 and EDTA. To quantify the oxidant yield, excess amount of methanol was employed, and the formation of its oxidation product, formaldehyde (HCHO), was monitored. The concentration of HCHO in the nZVI/O2 system rapidly reached the saturation value, whereas that in the mZVI/O2 system gradually increased throughout the entire reaction time. The mZVI/O2 system exhibited higher yields of HCHO than the nZVI/O2 system under both acidic and neutral pH conditions. The higher oxidant yields in the mZVI/O2 system are mainly attributed to the less reactivity of the mZVI surface with hydrogen peroxide (H2O2) relative to the surface of nZVI, which minimize the loss of H2O2 by ZVI (i.e., the two-electron reduction of H2O2 into water). In addition, the slow dissolution of Fe(II) from mZVI was found to be partially responsible for the higher oxidant yields at neutral pH. PMID:24361799

  12. Arsenic stabilization by zero-valent iron, bauxite residue, and zeolite at a contaminated site planting Panax notoginseng.

    PubMed

    Yan, X L; Lin, L Y; Liao, X Y; Zhang, W B; Wen, Y

    2013-10-01

    Panax notoginseng (Burk.) F.H. Chen, a rare traditional Chinese medicinal herb, is a widely used phytomedicine used all over the world. In recent years, the arsenic contamination of the herb and its relative products becomes a serious problem due to elevated soil As concentration. This study aimed to evaluate the effects of different types and dosages of amendments on As stabilization in soil and its uptake by P. notoginseng. Results showed that comparing to control treatment, the As concentrations of P. notoginseng declined by 49-63%, 43-61% and 52-66% in 0.25% zero-valent iron (Fe(0)), 0.5% bauxite residue, and 1% zeolite treatment, respectively; whereas the biomasses were elevated by 62-116%, 45-152% and 114-265%, respectively. The As(III) proportions of P. notoginseng increased by 8%, 9%, and 8%, and the transfer factors of As from root to shoot increased by 37%, 42% and 84% in the optimal treatments of Fe(0), bauxite residue, and zeolite. For soil As, all the three amendments could transform the non-specifically adsorbed As fraction to hydrous oxides Fe/Al fractions (by Fe(0) and red mud) or specifically adsorbed As fraction (by zeolite), therefore reduced the bioavailability of soil As. With a comprehensive consideration of stabilization efficiency, plant growth, environmental influence, and cost, Fe(0) appeared to be the best amendment, and zeolite could also be a good choice. In conclusion, this study was of significance in developing As contamination control in P. notoginseng planting areas, and even other areas for medicinal herb growing. PMID:23871591

  13. Reductive dehalogenation of trichloroethylene with zero-valent iron: Surface profiling microscopy and rate enhancement studies

    SciTech Connect

    Gotpagar, J.; Lyuksyutov, S.; Cohn, R.; Grulke, E.; Bhattacharyya, D.

    1999-11-23

    Mechanistic aspects of the reductive dehalogenation of trichloroethylene using zerovalent iron are studied with three different surface characterization techniques. These include scanning electron microscopy, surface profilometry, and atomic force microscopy. It was found that the pretreatment of an iron surface by chloride ions causes enhancement in the initial degradation rates. This enhancement was attributed to the increased roughness of the iron surface due to crevice corrosion obtained by pretreatment. The results indicate that the fractional active site concentration for the reactive sorption of trichloroethylene is related to the number of defects/abnormalities present on the surface of the iron. This was elucidated with the help of atomic force microscopy. Two possible mechanisms include (1) a direct hydrogenation in the presence of defects acting as catalyst and (2) an enhancement due to the two electrochemical cells operating in proximity to each other. The result of this study has potential for further research to achieve an increase in the reaction rates by surface modifications in a practical scenario.

  14. Deployment of an innovative thermally enhanced soil mixing process augmented with zero-valent iron.

    SciTech Connect

    Lynch, P. L.

    1999-01-15

    An innovative in-situ soil treatment process, referred to as soil mixing/thermally enhanced soil vapor extraction (SM/TESVE), was used to remediate the 317 Area of Argonne National Laboratory-East (i.e., Argonne), which is contaminated with volatile organic compounds (VOCs). Following the initial soil treatment, polishing was required to reduce residual concentrations of contaminants. A study of polishing methods was conducted. It determined that injecting metallic iron particles into the soil, in conjunction with soil mixing, would reduce residual VOC concentrations more effectively than the original conventional soil ventilation approach. After the effectiveness of iron injection was verified, it replaced the soil ventilation step. The modified process involved mixing the soil while hot air and steam were injected into it. Off-gases were captured in a hood over the treatment area. During this process, an iron slurry, consisting of up to 50% iron particles in water with guar gum added as a thickening agent, was injected and mixed into the soil by the mixing equipment. Approximately 6,246 m{sup 3} (8, 170 yd{sup 3}) of soil was treated during this project. Confirmatory samples were then collected. In these samples, VOC concentrations were usually reduced by more than 80%.

  15. Stimulation of peanut seedling development and growth by zero-valent iron nanoparticles at low concentrations.

    PubMed

    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 (320 μmol/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

  16. 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

  17. Coupling of zero valent iron and biobarriers for remediation of trichloroethylene in groundwater.

    PubMed

    Teerakun, Mullika; Reungsang, Alissara; Lin, Chien-Jung; Liao, Chih-Hsiang

    2011-01-01

    This study attempted to construct a three series barrier system to treat high concentrations of trichloroethylene (TCE; 500 mg/L) in synthetic groundwater. The system consisted of three reactive barriers using iron fillings as an iron-based barrier in the first column, sugarcane bagasse mixed with anaerobic sludge as an anaerobic barrier in the second column, and a biofilm coated on oxygen carbon inducer releasing material as an aerobic barrier in the third column. In order to evaluate the extent of removal of TCE and its metabolites in the aquifer down gradient of the barrier system, a fourth column filled with sand was applied. Residence time of the system was investigated by a bromide tracer test. The results showed that residence time in the column system of the control set and experimental set were 23.62 and 29.99 days, respectively. The efficiency of the three series barrier system in removing TCE was approximately 84% in which the removal efficiency of TCE by the iron filling barrier, anaerobic barrier and aerobic barrier were 42%, 16% and 25%, respectively, cis-Dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene and chloride ions were observed as metabolites following TCE degradation. The presence of chloride ions in the effluent from the column system indicated the degradation of TCE. However, cis-DCE and VC were not fully degraded by the proposed barrier system which suggested that another remediation technology after the barrier treatment such as air sparging and adsorption by activated carbon should be conducted. PMID:21793396

  18. Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

    SciTech Connect

    Yuxin Wu; Roelof Versteeg; Lee Slater; Doug Labrecque

    2009-05-01

    Calcium carbonate is a major secondary mineral precipitate that influences PRB reactivity and hydraulic performance. In this study, we conducted column experiments to investigate electrical signatures resulting from concurrent CaCO3 and iron oxides precipitation in two simulated PRB media. Solid phase analysis identified CaCO3 (calcite and aragonite) as a major mineral phase throughout the columns, with magnetite being another major phase present close to the influent. Electrical measurements revealed a consistent decrease in conductivity and polarization magnitude of both columns, suggesting that the electrically insulating CaCO3 dominates the electrical response despite the presence of both electrically conductive iron oxides and CaCO3 precipitates. SEM/EDX imaging suggests that the electrical properties result from the geometrical arrangement of the mineral phases. The CaCO3 forms an insulating film on ZVI/magnetite surfaces, which we assume restricts redox-driven transfer of electric charge between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss.

  19. Field-scale transport and transformation of carboxymethylcellulose-stabilized nano zero-valent iron.

    PubMed

    Johnson, Richard L; Nurmi, James T; O'Brien Johnson, Graham S; Fan, Dimin; O'Brien Johnson, Reid L; Shi, Zhenqing; Salter-Blanc, Alexandra J; Tratnyek, Paul G; Lowry, Gregory V

    2013-02-01

    The fate of nano zerovalent iron (nZVI) during subsurface injection was examined using carboxymethylcellulose (CMC) stabilized nZVI in a very large three-dimensional physical model aquifer with detailed monitoring using multiple, complementary detection methods. A fluorescein tracer test in the aquifer plus laboratory column data suggested that the very-aggressive flow conditions necessary to achieve 2.5 m of nZVI transport could be obtained using a hydraulically constrained flow path between injection and extraction wells. However, total unoxidized nZVI was transported only about 1 m and <2% of the injected nZVI concentration reached that distance. The experimental data also indicated that groundwater flow changed during injection, likely due to hydrogen bubble formation, which diverted the nZVI away from the targeted flow path. The leading edge of the iron plume became fully oxidized during transport. However, within the plume, oxidation of nZVI decreased in a fashion consistent with progressive depletion of aquifer "reductant demand". To directly quantify the extent of nZVI transport, a spectrophotometric method was developed, and the results indicated that deployment of unoxidized nZVI for groundwater remediation will likely be difficult. PMID:23311327

  20. Effect of Structural Transformation of Nanoparticulate Zero-Valent Iron on Generation of Reactive Oxygen Species.

    PubMed

    He, Di; Ma, Jinxing; Collins, Richard N; Waite, T David

    2016-04-01

    While it has been recognized for some time that addition of nanoparticlate zerovalent iron (nZVI) to oxygen-containing water results in both corrosion of Fe(0) and oxidation of contaminants, there is limited understanding of either the relationship between transformation of nZVI and oxidant formation or the factors controlling the lifetime and extent of oxidant production. Using Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, we show that while nZVI particles are transformed to ferrihydrite then lepidocrocite in less than 2 h, oxidant generation continues for up to 10 h. The major products (Fe(II) and H2O2) of the reaction of nZVI with oxygenated water are associated, for the most part, with the surface of particles present with these surface-associated Fenton reagents inducing oxidation of a target compound (in this study, (14)C-labeled formate). Effective oxidation of formate only occurred after formation of iron oxides on the nZVI surface with the initial formation of high surface area ferrihydrite facilitating rapid and extensive adsorption of formate with colocation of this target compound and surface-associated Fe(II) and H2O2 apparently critical to formate oxidation. Ongoing formate oxidation long after nZVI is consumed combined with the relatively slow consumption of Fe(II) and H2O2 suggest that these reactants are regenerated during the nZVI-initiated heterogeneous Fenton process. PMID:26958862

  1. Effect of zero valent iron nanoparticles to Eisenia fetida in three soil types.

    PubMed

    Yirsaw, Biruck Desalegn; Mayilswami, Srinithi; Megharaj, Mallavarapu; Chen, Zuliang; Naidu, Ravi

    2016-05-01

    In this study, the influence of soil types on the effect of the commercial form of C-nZVI on tissue concentrations, cellular component, reproduction outcome in Eisenia fetida, and the soil health was investigated. C-nZVI at concentration level of 3 g kg(-1) soil showed no effect on the survival of E. fetida in the three soil types. However, varying effects such as concentration-dependent increase in tissue iron concentration, lipid peroxidation, and damage to DNA molecules by C-nZVI were observed. C-nZVI at an exposure concentration of 60 mg kg(-1) soil induced oxidative stress in E. fetida. Tissue Fe concentration appeared correlated to the DNA damage. Oxidative stress and DNA damage may explain the toxicity mechanisms of nZVI to E. fetida. Graphical Abstract Reactive oxygen species induced by nZVI. PMID:26856861

  2. Diversity of Contaminant Reduction Reactions by Zero-Valent Iron: Role of the Reductate

    SciTech Connect

    Miehr, R; Tratnyek, Paul G.; Bandstra, J; Scherer, Michelle; Alowitz, M; Bylaska, Eric J.

    2004-01-01

    The reactions of 8 model contaminants with 9 types of granular Fe(0) were studied in batch experiments using consistent experimental conditions. The model contaminants (herein referred to as reductates because they were reduced by the iron metal) included cations (Cu2+), anions (CrO42-; NO3-; and 5,5,7,7-indigotetrasulfonate), and neutral species (2-chloroacetophenone; 2,4,6-trinitrotoluene; carbon tetrachloride; and trichloroethene). The diversity of this range of reductates offers a uniquely broad perspective on the reactivity of Fe(0). Rate constants for disappearance of the reductates vary over as much as 4 orders of magnitude for particular reductates (due to differences in the 9 types of iron) but differences among the reductates were even larger, ranging over almost 7 orders of magnitude. Various ways of summarizing the data all suggest that relative reactivities with Fe(0) varies in the order: Cu2, I4S > 2CAP, TNT > CT, Cr6 > TCE > NO3. Although the reductate h as the largest effect on disappearance kinetics, more subtle differences in reactivity due to the type of Fe(0) suggests that removal of Cr6 and NO3 (the inorganic anions) involves adsorption to oxides on the Fe(0), whereas the disappearance kinetics of all other types of reductants is favored by reduction on comparatively oxide-free metal. Correlation analysis of the disappearance rate constants using descriptors of the reductates calculated by molecular modeling (energies of the lowest unoccupied molecular orbitals, LUMO, highest occupied molecular orbitals, HOMO, and HOMO-LUMO gaps) showed that reactivities generally increase with decreasing ELUMO and increasing EGAP (and, therefore, increasing chemical hardness h).

  3. Selenate removal by zero-valent iron in oxic condition: the role of Fe(II) and selenate removal mechanism.

    PubMed

    Yoon, In-Ho; Bang, Sunbaek; Kim, Kyoung-Woong; Kim, Min Gyu; Park, Sang Yoon; Choi, Wang-Kyu

    2016-01-01

    In this study, batch experiments were conducted to investigate the effect of the concentration of ferrous [Fe(II)] ions on selenate [Se(VI)] removal using zero-valent iron (ZVI). The mechanism of removal was investigated using spectroscopic and image analyses of the ZVI-Fe(II)-Se(VI) system. The test to remove 50 mg/L of Se(VI) by 1 g/L of ZVI resulted in about 60% removal of Se(VI) in the case with absence of Fe(II), but other tests with the addition of 50 and 100 mg/L of the Fe(II) had increased the removal efficiencies about 93 and 100% of the Se(VI), respectively. In other batch tests with the absence of ZVI, there were little changes on the Se(VI) removal by the varied concentration of the Fe(II). From these results, we found that Fe(II) ion plays an accelerator for the reduction of Se(VI) by ZVI with the stoichiometric balance of 1.4 (=nFe(2+)/nSe(6+)). Under anoxic conditions, the batch test revealed about 10% removal of the Se(VI), indicating that the presence of dissolved oxygen increased the kinetics of Se(VI) removal due to the Fe(II)-containing oxides on the ZVI, as analyzed by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectra also showed that the reductive process of Se(VI) to Se(0)/Se(-II) occurred in the presence of the both ZVI and Fe(II). The final product of iron corrosion was lepidocrocite (γ-FeOOH), which acts as an electron transfer barrier from Fe(0) core to Se(VI). Therefore, the addition of Fe(II) enhanced the reactivity of ZVI through the formation of iron oxides (magnetite) favoring electron transfer during the removal of Se(VI), which was through the exhaustion of the Fe(0) core reacted with Se(VI). PMID:25943509

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

    PubMed

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

    2015-07-21

    A pilot scale injection of nanoscale zerovalent iron (nZVI) stabilized with carboxymethyl cellulose (CMC) was performed at an active field site contaminated with a range of chlorinated volatile organic compounds (cVOC). The cVOC concentrations and microbial populations were monitored at the site before and after nZVI injection. The remedial injection successfully reduced parent compound concentrations on site. A period of abiotic degradation was followed by a period of enhanced biotic degradation. Results suggest that the nZVI/CMC injection created conditions that stimulated the native populations of organohalide-respiring microorganisms. The abundance of Dehalococcoides spp. immediately following the nZVI/CMC injection increased by 1 order of magnitude throughout the nZVI/CMC affected area relative to preinjection abundance. Distinctly higher cVOC degradation occurred as a result of the nZVI/CMC injection over a 3 week evaluation period when compared to control wells. This suggests that both abiotic and biotic degradation occurred following injection. PMID:26090687

  5. Iron-mediated oxidation of arsenic(III) by oxygen and hydrogen peroxide: dispersed versus resin-supported zero-valent iron.

    PubMed

    Du, Qiong; Zhou, Lixia; Zhang, Shujuan; Pan, Bingcai; Lv, Lu; Zhang, Weiming; Zhang, Quanxing

    2014-08-15

    The goal of this study is to assess the differences in As(III) removal kinetics and mechanisms between dispersed zero-valent iron (d-ZVI) and resin-supported zero-valent iron (D201-ZVI) in the presence of dissolved oxygen and hydrogen peroxide. Experimental results show that As(III) could be removed by all the studied systems (d-ZVI/O2, d-ZVI/H2O2, D201-ZVI/O2, D201-ZVI/H2O2). The d-ZVI/H2O2 system was more efficient than D201-ZVI/H2O2 for the oxidation of As(III). Similar trends were observed in O2 system for both solids. The kinetic behaviors as well as the influence of a hydroxyl radical scavenger (2-propanol) on the oxidation of As(III) at different pH suggest that the oxidation of As(III) in the d-ZVI/O2 and d-ZVI/H2O2 systems occurred mainly through Fenton-like reactions. The oxidation of As(III) in the D201-ZVI/O2 and D201-ZVI/H2O2 systems might be expected as follows: As(III) was firstly adsorbed onto the surface of the D201-ZVI, and then oxidation may proceed mainly through a non-Fenton mechanism that directly converts H2O2 into O2 and H2O. In addition, certain iron oxides in the D201-ZVI could also serve as oxidants for As(III) oxidation. The significant differences between the dispersed and supported ZVIs suggest that the supporting matrix interfered in the removal process, which deserves a further investigation. PMID:24910051

  6. Remediation of chromate-contaminated ground water using zero-valent iron: Field test at USCG Support Center, Elizabeth City, North Carolina

    SciTech Connect

    Puls, R.W.; Paul, C.J.; Powell, R.M.

    1996-12-31

    A field test was conducted near an old hard-chrome plating facility on the USCG Support Center near Elizabeth City, North Carolina, to evaluate the in situ remediation of ground water contaminated by hexavalent chromium using a passive permeable reactive barrier composed of a zero-valent iron-sand-aquifer material mixture. The remedial effectiveness of this innovative in situ technology was monitored over a one-year period. The success of this small-scale test has prompted a full-scale implementation of the technology at the site for late Spring 1996.

  7. The effects of flow rate and concentration on nitrobenzene removal in abiotic and biotic zero-valent iron columns.

    PubMed

    Yin, Weizhao; Wu, Jinhua; Huang, Weilin; Li, Yongtao; Jiang, Gangbiao

    2016-08-01

    This study investigated the effects of varying nitrobenzene (NB) loadings via increasing flow rate or influent NB concentration mode on the removal efficiency in zero-valent iron (ZVI) columns sterilized (abiotic) or preloaded with acclimated microorganisms (biotic). It was shown that physical sequestration via adsorption/co-precipitation and reductive transformation of NB to aniline (AN) were the two major mechanisms for the NB removal in both abiotic and biotic ZVI columns. The NB removal efficiency decreased in both columns as the flow rate increased from 0.25 to 1.0mLmin(-1) whereas the AN recovery increased accordingly, with relatively high AN recovery observed at the flow rate of 1.0mLmin(-1). At the constant flow rate of 0.5mLmin(-1), increasing influent NB concentration from 80 to 400μmolL(-1) resulted in decreasing of the overall NB removal efficiency from 79.5 to 48.6% in the abiotic column and from 85.6 to 62.5% in the biotic column. The results also showed that the sequestration capacity and chemical reduction capacity were respectively 72% and 157.6% higher in the biotic column than in the abiotic column at the same tested hydraulic conditions and NB loadings. The optimal flow rates and influent NB concentrations were at 0.5mLmin(-1) and 80μmolL(-1) for the abiotic column and 2.0mLmin-1 and 240μmolL(-1) for the biotic column, respectively. This study indicated that microorganisms not only enhanced overall reduction of NB, but also facilitated NB sequestration within the porous media and that the optimal loading conditions for overall removal, sequestration, and reduction of NB may be different. Optimal operation conditions should be found for preferred sequestration or transformation (or both) of the target contaminants to meet different goals of groundwater remediation with the ZVI-PRB systems. PMID:27093118

  8. Modeling Polymer Stabilized Nano-scale Zero Valent Iron Transport Experiments in Porous Media to Understand the Transport Behavior

    NASA Astrophysics Data System (ADS)

    Mondal, P.; Krol, M.; Sleep, B. E.

    2015-12-01

    A wide variety of groundwater contaminants can be treated with nano-scale zero valent iron (nZVI). However, delivery of nZVI in the subsurface to the treatment zones is challenging as the bare nZVI particles have a higher tendency to agglomerate. The subsurface mobility of nZVI can be enhanced by stabilizing nZVI with polymer, such as carboxymethyl cellulose (CMC). In this study, numerical simulations were conducted to evaluate CMC stabilized nZVI transport behavior in porous media. The numerical simulations were based on a set of laboratory-scale transport experiments that were conducted in a two-dimensional water-saturated glass-walled sandbox (length - 55 cm; height - 45 cm; width - 1.4 cm), uniformly packed with silica sand. In the transport experiments: CMC stabilized nZVI and a non-reactive dye tracer Lissamine Green B (LGB) were used; water specific discharge and CMC concentration were varied; movements of LGB, and CMC-nZVI in the sandbox were tracked using a camera, a light source and a dark box. The concentrations of LGB, CMC, and CMC-nZVI at the sandbox outlet were analyzed. A 2D multiphase flow and transport model was applied to simulate experimental results. The images from LGB dye transport experiments were used to determine the pore water velocities and media permeabilities in various layers in the sand box. These permeability values were used in the subsequent simulations of CMC-nZVI transport. The 2D compositional simulator, modified to include colloid filtration theory (CFT), treated CMC as a solute and nZVI as a colloid. The simulator included composition dependent viscosity to account for CMC injection and mixing, and attachment efficiency as a fitting parameter for nZVI transport modeling. In the experiments, LGB and CMC recoveries were greater than 95%; however, CMC residence time was significantly higher than the LGB residence time and the higher CMC concentration caused higher pressure drops in the sandbox. The nZVI recovery was lower than 40

  9. Measuring the reactivity of commercially available zero-valent iron nanoparticles used for environmental remediation with iopromide.

    PubMed

    Schmid, Doris; Micić, Vesna; Laumann, Susanne; Hofmann, Thilo

    2015-10-01

    The high specific surface area and high reactivity of nanoscale zero-valent iron (nZVI) particles have led to much research on their application to environmental remediation. The reactivity of nZVI is affected by both the water chemistry and the properties of the particular type of nZVI particle used. We have investigated the reactivity of three types of commercially available Nanofer particles (from Nanoiron, s.r.o., Czech Republic) that are currently either used in, or proposed for use in full scale environmental remediation projects. The performance of one of these, the air-stable and thus easy-to-handle Nanofer Star particle, has not previously been reported. Experiments were carried out first in batch shaking reactors in order to derive maximum reactivity rates and provide a rapid estimate of the Nanofer particle's reactivity. The experiments were performed under near-natural environmental conditions with respect to the pH value of water and solute concentrations, and results were compared with those obtained using synthetic water. Thereafter, the polyelectrolyte-coated Nanofer 25S particles (having the highest potential for transport within porous media) were chosen for the experiments in column reactors, in order to elucidate nanoparticle reactivity under a more field-site realistic setting. Iopromide was rapidly dehalogenated by the investigated nZVI particles, following pseudo-first-order reaction kinetics that was independent of the experimental conditions. The specific surface area normalized reaction rate constant (kSA) value in the batch reactors ranged between 0.12 and 0.53Lm(-2)h(-1); it was highest for the uncoated Nanofer 25 particles, followed by the polyacrylic acid-coated Nanofer 25S and air-stable Nanofer Star particles. In the batch reactors all particles were less reactive in natural water than in synthetic water. The kSA values derived from the column reactor experiments were about 1000 times lower than those from the batch reactors, ranging

  10. Nano zero-valent iron impregnated on titanium dioxide nanotube array film for both oxidation and reduction of methyl orange.

    PubMed

    Yun, Dong-Min; Cho, Hyun-Hee; Jang, Jun-Won; Park, Jae-Woo

    2013-04-01

    Here, we demonstrated that nano zero-valent iron (nZVI) impregnated onto self-organized TiO(2) nanotube thin films exhibits both oxidation and reduction capacities in addition to the possible electron transfer from TiO(2) to nZVI. The TiO(2) nanotubes were synthesized by anodization of titanium foil in a two-electrode system. Amorphous TiO(2) (amTiO(2)) nanotubes were annealed at 450 °C for 1 h to produce crystalline TiO(2) (crTiO(2)) nanotubes. The nZVI particles were immobilized on the TiO(2) array film by direct borohydride reduction. Field emission scanning electron microscopy (FE-SEM) analysis of the crystalline TiO(2) nanotube with nZVI (nZVI/crTiO(2)) indicated that the nZVI particles with a mean particle diameter of 28.38 ± 11.81 nm were uniformly distributed onto entire crTiO(2) nanotube surface with a mean pore diameter of 75.24 ± 17.66 nm and a mean length of 40.07 μm. Environmental applicability of our proposed nZVI/TiO(2) nanotube thin films was tested for methyl orange (MO) degradation in the aqueous system with and without oxygen. Since oxygen could facilitate the nZVI oxidation and inhibit electron transfer from crTiO(2) to nZVI surface, MO degradation by nZVI/crTiO(2) in the presence of oxygen was significantly suppressed whereas nZVI/crTiO(2) in the absence of oxygen enhanced MO degradation. MO degradation rate by each sample without oxygen were in following order: nZVI/crTiO(2) (k(obs) = 0.311 min(-1)) > nZVI/amTiO(2) (k(obs) = 0.164 min(-1)) > crTiO(2) (k(obs) = 0.068 min(-1)). This result can be explained with a synergistic effect of the significant reduction by highly-dispersed nZVI particles on TiO(2) nanotubes as well as the electron transfer from the conduction band of crTiO(2) to the nZVI on the crTiO(2) for the degradation of MO. PMID:23375600

  11. Transport and retention of xanthan gum-stabilized microscale zero-valent iron particles in saturated porous media.

    PubMed

    Xin, Jia; Tang, Fenglin; Zheng, Xilai; Shao, Haibing; Kolditz, Olaf

    2016-01-01

    Microscale zero valent iron (mZVI) is a promising material for in-situ contaminated groundwater remediation. However, its usefulness has been usually inhibited by mZVI particles' low mobility in saturated porous media for sedimentation and deposition. In our study, laboratory experiments, including sedimentation studies, rheological measurements and transport tests, were conducted to investigate the feasibility of xanthan gum (XG) being used as a coating agent for mZVI particle stabilization. In addition, the effects of XG concentration, flow rate, grain diameter and water chemistry on XG-coated mZVI (XG-mZVI) particle mobility were explored by analyzing its breakthrough curves and retention profiles. It was demonstrated that XG worked efficiently to enhance the suspension stability and mobility of mZVI particles through the porous media as a shear thinning fluid, especially at a higher concentration level (3 g/L). The results of the column study showed that the mobility of XG-mZVI particles increased with an increasing flow rate and larger grain diameter. At the highest flow rate (2.30 × 10(-3) m/s) within the coarsest porous media (0.8-1.2 mm), 86.52% of the XG-mZVI flowed through the column. At the lowest flow rate (0.97 × 10(-4) m/s) within the finest porous media (0.3-0.6 mm), the retention was dramatically strengthened, with only 48.22% of the particles flowing through the column. The XG-mZVI particles appeared to be easily trapped at the beginning of the column especially at a low flow rate. In terms of two representative water chemistry parameters (ion strength and pH value), no significant influence on XG-mZVI particle mobility was observed. The experimental results suggested that straining was the primary mechanism of XG-mZVI retention under saturated condition. Given the above results, the specific site-related conditions should be taken into consideration for the design of a successful delivery system to achieve a compromise between

  12. Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: Effects of sorption, surfactants, and natural organic matter

    SciTech Connect

    Zhang, Man; He, Feng; Zhao, Dongye; Hao, Xiaodi

    2011-01-01

    Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, {approx}44% of TCE sorbed in the potting soil was degraded in 30 h, compared to {approx}82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1 x cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm

  13. Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter.

    PubMed

    Zhang, Man; He, Feng; Zhao, Dongye; Hao, Xiaodi

    2011-03-01

    Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼ 44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼ 82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1 × cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the

  14. Reductive dechlorination of organochlorine pesticides in soils from an abandoned manufacturing facility by zero-valent iron.

    PubMed

    Cong, Xin; Xue, Nandong; Wang, Shijie; Li, Keji; Li, Fasheng

    2010-07-15

    Several experiments and a model were constructed using conventional granular zero-valent iron (ZVI) particles as the reducing agent to study the reductive dechlorination characteristics of hexachlorocyclohexanes (HCHs) and dichlorodiphenyltrichloroethane (DDTs) in soils from a former pesticide-manufacturing site. The results showed that ZVI had good ability for the reductive dechlorination for both HCHs and DDTs. The reductive dechlorination of HCHs and DDTs proceeded at different rates. The pseudo first-order constants of HCHs were greater than those of DDTs. The reductive dechlorination rates in a descending order were gamma-HCH>delta-HCH>beta-HCH>alpha-HCH>o,p'-DDT>p,p'-DDT>p,p'-DDE. To discuss the major influential factors over the reductive dechlorination rates of HCHs and DDTs by ZVI, 22 quantum chemical descriptors were computed with the density functional theory at B3LYP/6-31G() level, which characterizes different molecular structures and physicochemical properties of HCHs and DDTs. A polyparameter linear free energy relationship (LFER) model was established, which correlates the reductive dechlorination properties of pollutants with their structural descriptors. Using the partial least squares (PLS) analysis, an optimal two-parameter LFER model was established. q(+) and q(Cl)(-) were more important factors in determining the dechlorination rate of OCPs in the chemical reductive reaction. This optimal model was stable and had good predictability. The model study also showed that the coefficient value of q(+) was 0.511, which positively correlated with the reductive dechlorination rate constant, whereas q(Cl)(-) was negatively correlated with it. The reductive dechlorination rate of pollutants appears to be limited mainly by the rate of dissolution in the aqueous phase. This model can be used to explain the degradation potential of organochlorine pesticides (OCPs) and the trend of residues changing during the soil remediation. Therefore, the study is of

  15. Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions.

    PubMed

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-04-01

    Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from -3.4±0.3 to -4.3±0.3‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from -7.0±0.4 to -13.6±1.2‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO4(-)). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO). PMID:26784392

  16. [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. PMID:26031079

  17. Removal of As, Mn, Mo, Se, U, V and Zn from groundwater by zero-valent iron in a passive treatment cell: reaction progress modeling

    NASA Astrophysics Data System (ADS)

    Morrison, Stan J.; Metzler, Donald R.; Dwyer, Brian P.

    2002-05-01

    Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe 3O 4), calcite (CaCO 3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH) 2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO 2, V 2O 3), sulfides (As 2S 3, ZnS), iron minerals (FeSe 2, FeMoO 4) and carbonate (MnCO 3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell.

  18. Application of response surface methodology (RSM) for the removal of methylene blue dye from water by nano zero-valent iron (NZVI).

    PubMed

    Khosravi, Morteza; Arabi, Simin

    2016-01-01

    In this study, iron zero-valent nanoparticles were synthesized, characterized and studied for removal of methylene blue dye in water solution. The reactions were mathematically described as the function of parameters such as nano zero-valent iron (NZVI) dose, pH, contact time and initial dye concentration, and were modeled by the use of response surface methodology. These experiments were carried out as a central composite design consisting of 30 experiments determined by the 2(4) full factorial designs with eight axial points and six center points. The results revealed that the optimal conditions for dye removal were NZVI dose 0.1-0.9 g/L, pH 3-11, contact time 20-100 s, and initial dye concentration 10-50 mg/L, respectively. Under these optimal values of process parameters, the dye removal efficiency of 92.87% was observed, which very close to the experimental value (92.21%) in batch experiment. In the optimization, R(2) and R(2)adj correlation coefficients for the model were evaluated as 0.96 and 0.93, respectively. PMID:27438238

  19. 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.

  20. Zero-valent iron and iron oxide-coated sand as a combination for removal of co-present chromate and arsenate from groundwater with humic acid.

    PubMed

    Mak, Mark S H; Rao, Pinhua; Lo, Irene M C

    2011-02-01

    The combination of zero-valent iron (Fe(0)) and iron oxide-coated sand (IOCS) was used to remove Cr(VI) and As(V) from groundwater in this study. The efficiency and the removal mechanism of Cr(VI) and As(V) by using this combination, with the influence of humic acid (HA), were investigated using batch experiments. Results showed that, compared to using Fe(0) or IOCS alone, the Fe(0)-IOCS can perform better on the removal of both Cr(VI) and As(V). Metal extraction studies showed that As(V) was mainly removed by IOCS and iron corrosion products while Cr(VI) was mainly removed by Fe(0) and its corrosion products. Competition was found between Cr(VI) and As(V) for the adsorption sites on the iron corrosion products. HA had shown insignificant effects on Cr(VI) removal but some effects on As(V) removal kinetics. As(V) was adsorbed on IOCS at the earlier stage, but adsorbed/coprecipitated with the iron corrosion products at the later stage. PMID:21130550

  1. 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. PMID:26803790

  2. Carboxymethyl Cellulose Stabilized Nano-scale Zero Valent Iron Transport in Porous Media: An Experimental and Modeling Study

    NASA Astrophysics Data System (ADS)

    Mondal, P.; Rrokaj, E.; Sleep, B. E.

    2013-12-01

    An experimental and modeling study is being conducted to evaluate carboxymethyl cellulose (CMC) stabilized nano-scale zero valent iron (nZVI) transport in porous media. A two-dimensional water-saturated glass-walled sandbox (55 cm x 45 cm x 1.3 cm in size) is being used for the study. The sandbox was packed uniformly with silica sand (600 μm to 425 μm grain diameter) under water-saturated conditions. From a series of hydraulic tests permeability of the system was calculated to be 1.0 x 10-12 m2. The transport tests are being conducted at pore-water velocities of 3, 5, and 10 m.d-1 to identify any shear-thinning effects associated with the CMC (MW = 90,000) solution, and effects of velocity on nZVI attachment to the porous media. A set of transport tests is being carried out using LissamineTM Green B (LGB) dye and CMC mixtures to characterize the CMC transport without nZVI. The transport tests are being conducted at various CMC concentrations ranging from 0.2% to 0.8% (w/v) to determine the effect of CMC concentration on nZVI transport under flowing conditions. For the CMC stabilized nZVI transport tests, nZVI is synthesized freshly in CMC solution before each experiment using sodium borohydride and ferrous sulfate. The synthesized nZVI concentrations range from 0.1 to 2.5 g.L-1. While higher nZVI concentration is desired for higher contaminant degradation, the higher nZVI concentration may cause greater aggregation and attachment to the porous media limiting the delivery distance for nZVI. In each transport experiment, the LGB-CMC solution or nZVI-CMC solution is injected into the sandbox as a pulse of 0.25 pore volume (PV). For LGB, the mass recovery was calculated to be ~ 96.5% indicating non-reactive transport in silica sand. The preliminary results also show that increased concentration of CMC (from 0.2% to 0.4 %) causes higher pressure drop across the sandbox, indicating that use of high CMC concentrations will limit injection rates with a corresponding

  3. Injection of polyelectrolytes enhances mobility of zero-valent iron nanoparticles in carbonate-rich porous media

    NASA Astrophysics Data System (ADS)

    Laumann, Susanne; Micić, Vesna; Schmid, Doris; Hofmann, Thilo

    2013-04-01

    The application of nanoscale zero-valent iron (nZVI) for in situ groundwater remediation has received increased attention as a beneficial and novel remediation technique. A precondition for effective nZVI field applications is its delivery to the contaminated source zones. This has proved to be difficult due to the limited mobility of nZVI, which remains one major obstacle to widespread utilization of this remediation approach (O'CAROLL ET AL., 2012). One important factor that controls mobility of nZVI is physical and chemical heterogeneity within the subsurface, such as mineralogical variations (KIM ET AL., 2012). In our previous study we showed that the nZVI transport in carbonate-rich porous media is significantly reduced compared to that in quartz porous media (LAUMANN ET AL., 2012). This is caused by favorable nZVI deposition onto carbonate sand and is attributed to the less negative surface charge of carbonate compared to that of quartz sand under the range of water chemical conditions typically encountered in aquifers. New strategies are therefore required to improve nZVI mobility in carbonate-rich porous media. One approach can be the injection of polyelectrolytes in the subsurface, which are expected to adsorb onto aquifer grains and provide greater repulsion between nZVI and the porous media. In this study the effect of co-injected polyelectrolytes on the transport of polyacrylic acid (PAA) coated nZVI in two model porous media, quartz and carbonate sands was evaluated. Column experiments were carried out aiming to evaluate mobility of PAA-nZVI co-injected with four polyelectrolytes, including natural organic matter (NOM), humic acid, carboxymethyl cellulose (CMC), and lignin sulfonate. The results demonstrated that the co-injection of the chosen polyelectrolytes does not influence mobility of PAA-nZVI in quartz sand; the breakthrough with co-injected polyelectrolytes was similar to that of the pure PAA-nZVI dispersion. This observation can be explained

  4. DEMONSTRATION OF IN SITU DEHALOGENATION OF DNAPL THROUGH INJECTION OF EMULSIFIED ZERO-VALIENT IRON AT LAUNCH COMPLEX 34 IN CAPE CANAVERAL AIR FORCE STATION, FLORIDA

    EPA Science Inventory

    The purpose of this project was to evaluate the technical and cost performance of emulsified zero-valent iron (EZVI) technology when applied to DNAPL contaminants in the saturated zone. This demonstration was conducted at Launch Complex 34, Cape Canaveral Air Force Station, FL, w...

  5. The ecotoxic potential of a new zero-valent iron nanomaterial, designed for the elimination of halogenated pollutants, and its effect on reductive dechlorinating microbial communities.

    PubMed

    Schiwy, Andreas; Maes, Hanna M; Koske, Daniel; Flecken, Mirkko; Schmidt, Kathrin R; Schell, Heico; Tiehm, Andreas; Kamptner, Andre; Thümmler, Silke; Stanjek, Helge; Heggen, Marc; Dunin-Borkowski, Rafal E; Braun, Jürgen; Schäffer, Andreas; Hollert, Henner

    2016-09-01

    The purpose of this study was to assess the ecotoxic potential of a new zero-valent iron nanomaterial produced for the elimination of chlorinated pollutants at contaminated sites. Abiotic dechlorination through the newly developed nanoscale zero-valent iron material and its effects on dechlorinating bacteria were investigated in anaerobic batch and column experiments. The aged, i.e. oxidized, iron material was characterization with dynamic light scattering, transmission electron microscopy and energy dispersive x-ray analysis, x-ray diffractometry and cell-free reactive oxygen measurements. Furthermore, it was evaluated in aerobic ecotoxicological test systems with algae, crustacean, and fish, and also applied in a mechanism specific test for mutagenicity. The anaerobic column experiments showed co-occurrence of abiotic and biological dechlorination of the common groundwater contaminant perchloroethene. No prolonged toxicity of the nanomaterial (measured for up to 300 days) towards the investigated dechlorinating microorganism was observed. The nanomaterial has a flake like appearance and an inhomogeneous size distribution. The toxicity to crustacean and fish was calculated and the obtained EC50 values were 163 mg/L and 458 mg/L, respectively. The nanomaterial showed no mutagenicity. It physically interacted with algae, which had implications for further testing and the evaluation of the results. Thus, the newly developed iron nanomaterial was slightly toxic in its reduced state but no prolonged toxicity was recorded. The aquatic tests revealed a low toxicity with EC50 values ≥ 163 mg/L. These concentrations are unlikely to be reached in the aquatic environment. Hence, this nanomaterial is probably of no environmental concern not prohibiting its application for groundwater remediation. PMID:27317494

  6. An Experimental Study of Micron-Size Zero-Valent Iron Emplacement in Permeable Porous Media Using Polymer-Enhanced Fluids

    SciTech Connect

    Oostrom, Mart; Wietsma, Thomas W.; Covert, Matthew A.; Vermeul, Vince R.

    2005-12-22

    At the Hanford Site, an extensive In Situ Redox Manipulation (ISRM) permeable reactive barrier was installed to prevent chromate from reaching the Columbia River. However, chromium has been detected in several wells, indicating a premature loss of the reductive capacity in the aquifer. One possible cause for premature chromate breakthrough is associated with the presence of high-permeability zones in the aquifer. In these zones, groundwater moves relatively fast and is able to oxidize iron more rapidly. There is also a possibility that the high-permeability flow paths are deficient in reducing equivalents (e.g. reactive iron), required for barrier performance. One way enhancement of the current barrier reductive capacity can be achieved is by the addition of micron-scale zero-valent iron to the high-permeability zones within the aquifer. The potential emplacement of zero-valent iron (Fe0) into high-permeability Hanford sediments (Ringold Unit E gravels) using shear-thinning fluids containing polymers was investigated in three-dimensional wedge-shaped aquifer models. Polymers were used to create a suspension viscous enough to keep the Fe0 in solution for extended time periods to improve colloid movement into the porous media without causing a permanent detrimental decrease in hydraulic conductivity. Porous media were packed in the wedge-shaped flow cell to create either a heterogeneous layered system with a high-permeability zone in between two low-permeability zones or a high-permeability channel surrounded by low-permeability materials. The injection flow rate, polymer type, polymer concentration, and injected pore volumes were determined based on preliminary short- and long-column experiments.

  7. Synthesis of zeolite-supported microscale zero-valent iron for the removal of Cr(6+) and Cd(2+) from aqueous solution.

    PubMed

    Kong, Xiangke; Han, Zhantao; Zhang, Wei; Song, Le; Li, Hui

    2016-03-15

    Zeolite-supported microscale zero-valent iron (Z-mZVI) was synthesized and used to remove heavy metal cation (Cd(2+)) and anion (Cr(6+)) from aqueous solution. Transmission electron microscope (TEM) confirmed that mZVI (100-200 nm) has been successfully loaded and efficiently dispersed on zeolite. Atomic absorption Spectroscopy (AAS) revealed the amount of stabilized mZVI was about 1.3 wt.%. The synthesized Z-mZVI has much higher reduction ability and adsorption capacity for Cr(6+) and Cd(2+) compared to bare nanoscale zero-valent iron (nZVI) and zeolite. Above 77% Cr(6+) and 99% Cd(2+) were removed by Z-mZVI, while only 45% Cr(6+) and 9% Cd(2+) were removed by the same amount iron of nZVI, and 1% Cr(6+) and 39% Cd(2+) were removed by zeolite alone with an initial concentration of 20 mg/L Cr(6+) and 200 mg/L Cd(2+). The removal of Cr(6+) by Z-mZVI follows the pseudo first-order kinetics model, and X-ray photoelectron spectroscopy (XPS) analysis confirmed that Cr(6+) was reduced to Cr(3+) and immobilized on the surface of Z-mZVI. The removal mechanisms for Cr(6+) include reduction, adsorption of Cr(3+) hydroxides and/or mixed Fe(3+)/Cr(3+) (oxy)hydroxides. The pseudo-second-order kinetic model indicated that chemical sorption might be rate-limiting in the sorption of Cd(2+) by Z-mZVI. This synthesized Z-mZVI has shown the potential as an efficient and promising reactive material for removing various heavy metals from wastewater or polluted groundwater. PMID:26731307

  8. 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...

  9. Estimate of the optimum weight ratio in zero-valent iron/pumice granular mixtures used in permeable reactive barriers for the remediation of nickel contaminated groundwater.

    PubMed

    Calabrò, P S; Moraci, N; Suraci, P

    2012-03-15

    This paper presents the results of laboratory column tests aimed at defining the optimum weight ratio of zero-valent iron (ZVI)/pumice granular mixtures to be used in permeable reactive barriers (PRBs) for the removal of nickel from contaminated groundwater. The tests were carried out feeding the columns with aqueous solutions of nickel nitrate at concentrations of 5 and 50 mg/l using three ZVI/pumice granular mixtures at various weight ratios (10/90, 30/70 and 50/50), for a total of six column tests; two additional tests were carried out using ZVI alone. The most successful compromise between reactivity (higher ZVI content) and long-term hydraulic performance (higher Pumice content) seems to be given by the ZVI/pumice granular mixture with a 30/70 weight ratio. PMID:21885195

  10. Permeable reactive barrier of coarse sand-supported zero valent iron for the removal of 2,4-dichlorophenol in groundwater.

    PubMed

    Gao, Weichun; Zhang, Yongxiang; Zhang, Xiaoye; Duan, Zhilong; Wang, Youhao; Qin, Can; Hu, Xiao; Wang, Hao; Chang, Shan

    2015-11-01

    In this study, coarse sand-supported zero valent iron (ZVI) composite was synthesized by adding sodium alginate to immobilize. Composite was detected by scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray fluorescence (XRF). SEM results showed that composite had core-shell structure and a wide porous distribution pattern. The synthesized composite was used for degradation of 2,4-dichlorophenol (2,4-DCP) contamination in groundwater. Experimental results demonstrated that degradation mechanism of 2,4-DCP using coarse sand-supported ZVI included adsorption, desorption, and dechlorination. 2,4-DCP adsorption was described as pseudo-second-order kinetic model. It was concluded that dechlorination was the key reaction pathway, ZVI and hydrogen are prime reductants in dechlorination of 2,4-DCP using ZVI. PMID:26104904

  11. The fate of iron nanoparticles in environmental waters treated with nanoscale zero-valent iron, FeONPs and Fe3O4NPs.

    PubMed

    Peeters, Kelly; Lespes, Gaëtane; Zuliani, Tea; Ščančar, Janez; Milačič, Radmila

    2016-05-01

    Among the different nanoparticles (NPs) that are used in the remediation of contaminated environmental waters, iron nanoparticles (FeNPs) are the most frequently applied. However, if these FeNPs remain in the waters after the treatment, they can cause a hazard to the environment. In this work the time dependent size distribution of iron particles was investigated in Milli-Q water, forest spring water and landfill leachate after a variety of FeNP treatments. The efficiency of the metal removal by the FeNPs was also examined. The concentrations of the metals in the aqueous samples were determined before and after the nano-remediation by inductively coupled plasma mass spectrometry (ICP-MS). The data revealed that the settling and removal of the FeNPs after the treatment of the waters was related to the sample characteristics and the ways of dispersing the NPs. When mixing was used for the dispersion, the nano zero-valent iron (nZVI), FeONPs and Fe3O4NPs settled quickly in the Milli-Q water, the forest spring water and the landfill leachate. Dispersion with tertramethylammonium hydroxide (TMAH) resulted in a slower settling of the iron aggregates. In the Milli-Q and forest spring waters treated with FeONPs and dispersed by TMAH, the nanosized iron remained in solution as long as 24 h after the treatment and could represent a potential threat in environmental waters with a low ionic strength. The removal of the metals strongly depended on the type of FeNPs, the chemical speciation of the elements and the sample matrix. If the FeNPs are contaminated by a particular metal, this contaminant could be, during the NPs treatment, released into the water that is being remediated. PMID:26971807

  12. 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. PMID:26267258

  13. Inhibition of nitrate reduction by NaCl adsorption on a nano-zero-valent iron surface during a concentrate treatment for water reuse.

    PubMed

    Hwang, Yuhoon; Kim, Dogun; Shin, Hang-Sik

    2015-01-01

    Nanoscale zero-valent iron (NZVI) has been considered as a possible material to treat water and wastewater. However, it is necessary to verify the effect of the matrix components in different types of target water. In this study, different effects depending on the sodium chloride (NaCl) concentration on reductions of nitrates and on the characteristics of NZVI were investigated. Although NaCl is known as a promoter of iron corrosion, a high concentration of NaCl (>3 g/L) has a significant inhibition effect on the degree of NZVI reactivity towards nitrate. The experimental results were interpreted by a Langmuir-Hinshelwood-Hougen-Watson reaction in terms of inhibition, and the decreased NZVI reactivity could be explained by the increase in the inhibition constant. As a result of a chloride concentration analysis, it was verified that 7.7-26.5% of chloride was adsorbed onto the surface of NZVI. Moreover, the change of the iron corrosion product under different NaCl concentrations was investigated by a surface analysis of spent NZVI. Magnetite was the main product, with a low NaCl concentration (0.5 g/L), whereas amorphous iron hydroxide was observed at a high concentration (12 g/L). Though the surface was changed to permeable iron hydroxide, the Fe(0) in the core was not completely oxidized. Therefore, the inhibition effect of NaCl could be explained as the competitive adsorption of chloride and nitrate. PMID:25358487

  14. [Effects of pH value on the adsorption and degradation of 2, 4-DCP by nanoscale zero-valent iron].

    PubMed

    Feng, Li; Ge, Xiao-Peng; Wang, Dong-Sheng; Tang, Hong-Xiao

    2012-01-01

    To evaluate the effect of pH on the degradation of 2,4-DCP by zero-valent iron nanoparticles (with the particle size of 30-40 nm in diameter) samples were taken for TEM, SEM-EDX, and ICP-OES analysis and investigated on the particle morphology changes and 2,4-DCP removal under different pH conditions. It is shown that iron nanoparticles agglomerate from individual particles and tiny clusters into massive aggregate assemblies with their surfaces oxidized and coated by the needle-like rotten iron oxide products (FeOOH) in the degradation process, which will block up a further reaction of 2,4-DCP dechlorination, while the low pH value condition in acidic system can effectively suppress particles aggregation and the surface oxidation, although iron loss in the solid phase is somehow inevitable. Large quantity of Fe2+ ions soaked out from iron nanoparticles significantly promote 2,4-DCP removal by reduction, and the solution pH tends to go up in the reaction process. Acidic conditions facilitate 2,4-DCP dechlorination, and the removal efficiency became higher with the pH reduced, in which 90% of 2,4-DCP removal is reached in 24 h under the pH value of 3. PMID:22452195

  15. Effects of hardness and alkalinity on the removal of arsenic(V) from humic acid-deficient and humic acid-rich groundwater by zero-valent iron.

    PubMed

    Mak, Mark S H; Rao, Pinhua; Lo, Irene M C

    2009-09-01

    The effects of hardness (Ca(2+)) and alkalinity (HCO(3)(-)) on arsenic(V) removal from humic acid (HA)-deficient and HA-rich groundwater by zero-valent iron (Fe(0)) were investigated using batch experiments. Arsenic, in general, is removed from groundwater possibly by adsorption and co-precipitation with the iron corrosion products. However, in the co-presence of HCO(3)(-) and Ca(2+), the removal rate of arsenic increased with increasing concentrations of either Ca(2+) or HCO(3)(-). It was observed that the removal of arsenic was significantly enhanced by the formation of CaCO(3) as a nucleation seed for the growth of large iron (hydr)oxide particles. In the co-existence of Ca(2+), HCO(3)(-) and HA, the presence of HA diminished the positive role of Ca(2+) due to the formation of Fe-humate complexes in solution and delaying of the formation of CaCO(3). As a result, the formation of the large iron (hydr)oxide particles was inhibited in the earlier stage which, in turn, affected the removal of arsenic. However, after the formation of CaCO(3) and the subsequent growth of such particles, the presence of large iron (hydr)oxide particles resulted in the rapid removing of arsenic and Fe-humate by adsorption and/or co-precipitation. PMID:19580986

  16. Nanoscale zero-valent iron for the removal of Zn2+, Zn(II)-EDTA and Zn(II)-citrate from aqueous solutions.

    PubMed

    Kržišnik, Nina; Mladenovič, Ana; Škapin, Andrijana Sever; Škrlep, Luka; Ščančar, Janez; Milačič, Radmila

    2014-04-01

    The parameters which influence the removal of different zinc (Zn) species: Zn(2+), Zn(II)-EDTA and Zn(II)-citrate from aqueous solutions by nanoparticles of zero-valent iron (nZVI) were investigated at environmental relevant pH values. Untreated, surface modified and silica-fume supported nZVI were applied at different iron loads and contact times to Zn solutions, which were buffered to pH 5.3, 6.0 and 7.0. The results revealed that pH, the type of nZVI, the iron load, the contact time, and the Zn species all had a significant influence on the efficiency of removal. Zn(2+), Zn(II)-EDTA and Zn(II)-citrate were the most effectively removed from aqueous solutions by untreated nZVI. Zn(2+) removal was governed mainly by adsorption onto precipitated iron oxides. Complete removal of Zn(2+) and Zn(II)-citrate was obtained at all pH values investigated. The removal of strong Zn(II)-EDTA complex was successful only at acidic pH, which favored degradation of Zn(II)-EDTA. Consequently, the released Zn(2+) was completely removed from the solution by adsorption onto iron oxides. PMID:24463023

  17. SCANNING ELECTRON ANALYSIS OF IRON FILINGS FROM A ZERO-VALENT IRON PERMEABLE BARRIER USED FOR GROUND WATER RESTORATION

    EPA Science Inventory

    Permeable iron reactive barriers have become a popular way to remediate contaminated ground water. Although this technology has been in use for about a decade, there is still little knowledge about long-term performance issues (l). One of the biggest concerns is the corrosion of ...

  18. Micron-Size Zero-Valent Iron Emplacement in Porous Media Using Polymer Additives: Column and Flow Cell Ex-periments

    SciTech Connect

    Oostrom, Mart; Wietsma, Thomas W.; Covert, Matthew A.; Vermeul, Vince R.

    2006-03-20

    At the Hanford Site, an extensive In Situ Redox Manipulation (ISRM) permeable reactive barrier was installed to prevent chromate from reaching the Columbia River. However, chromium has been detected in several wells, indicating a premature loss of the reductive capacity in the aquifer. Laboratory experiments have been conducted to investigate whether barrier reductive capacity can be enhanced by adding micron-scale zero-valent iron to the high-permeability zones within the aquifer using shear-thinning fluids containing polymers. Porous media were packed in a wedge-shaped flow cell to create either a heterogeneous layered system with a high-permeability zone between two low-permeability zones or a high-permeability channel sur-rounded by low-permeability materials. The injection flow rate, polymer type, polymer concentration, and injected pore volumes were determined based on preliminary short- and long-column experiments. The flow cell experiments indicated that iron concentration enhancements of at least 0.6% (w/w) could be obtained using moderate flow rates and injection of 30 pore volumes. The 0.6% amended Fe0 concentration would provide approximately 20 times the average reductive capacity that is provided by the dithionite-reduced iron in the ISRM barrier. Calculations show that a 1-m-long Fe0 amended zone with an average concentration of 0.6% w/w iron subject to a groundwater velocity of 1 m/day will have an estimated longevity of 7.2 years.

  19. Polyphosphate-enhanced production of reactive oxidants by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen: Yield and nature of oxidants.

    PubMed

    Kim, Hak-Hyeon; Lee, Hongshin; Kim, Hyung-Eun; Seo, Jiwon; Hong, Seok Won; Lee, Jeong-Yong; Lee, Changha

    2015-12-01

    The production of reactive oxidants from nanoparticulate zero-valent iron (nZVI) and ferrous ion (Fe(II)) in the presence of oxygen was greatly enhanced by the addition of tetrapolyphosphate (TPP) as an iron-chelating agent. Compared to other ligands, TPP exhibited superior activity in improving the oxidant yields. The nZVI/TPP/O2 and the Fe(II)/TPP/O2 systems showed similar oxidant yields with respect to the iron consumed, indicating that nZVI only serves as a source of Fe(II). The degradation efficacies of selected organic compounds were also similar in the two systems. It appeared that both hydroxyl radical (OH) and ferryl ion (Fe(IV)) are produced, and OH dominates at acidic pH. However, at pH > 6, little occurrence of hydroxylated oxidation products suggests that Fe(IV) is a dominant oxidant. The degradation rates of selected organic compounds by the Fe(II)/TPP/O2 system had two optimum points at pH 6 and 9, and these pH-dependent trends are likely attributed to the speciation of Fe(IV) with different reactivities. PMID:26093796

  20. Effect of nanoscale zero-valent iron and magnetite (Fe3O4) on the fate of metals during anaerobic digestion of sludge.

    PubMed

    Suanon, Fidèle; Sun, Qian; Mama, Daouda; Li, Jiangwei; Dimon, Biaou; Yu, Chang-Ping

    2016-01-01

    Anaerobic digestion (AD) is one of the most widely used processes to stabilize waste sewage sludge and produce biogas renewable energy. In this study, two different iron nanoparticles [nanoscale zero-valent iron (nZVI) and magnetite (Fe3O4)] were used in the mesophilic AD processes (37 ± 1 °C) to improve biogas production. In addition, changes of heavy metal (Cd, Co, Cu, Zn, Ni and Cr) speciation during AD of sludge with and without iron nanoparticles have been investigated. Concentrations of metals in the initial sludge were as follows: 63.1, 73.4, 1102.2, 2060.3, 483.9 and 604.1 mg kg(-1) (dry sludge basis) for Cd, Co, Cu, Zn, Ni and Cr, respectively. Sequential fractionation showed that metals were predominantly bonded to organic matter and carbonates in the initial sludge. Compared with AD without iron nanoparticles, the application of iron nanoparticles (at dose of 0.5% in this study) showed positive impact not only on biogas production, but also on improvement of metals stabilization in the digestate. Metals were found concentrated in Fe-Mn bound and residual fractions and little was accumulated in the liquid digestate and most mobile fractions of solid digestate (water soluble, exchangeable and carbonates bound). Therefore, iron nanoparticles when properly used, could improve not only biogas yield, but also regulate and control the mobilization of metals during AD process. However, our study also observed that iron nanoparticles could promote the immobilization of phosphorus within the sludge during AD, and more research is needed to fully address the mechanism behind this phenomenon and the impact on future phosphorus reuse. PMID:26613183

  1. Environmental benefits and risks of zero-valent iron nanoparticles (nZVI) for in situ remediation: risk mitigation or trade-off?

    PubMed

    Grieger, Khara D; Fjordbøge, Annika; Hartmann, Nanna B; Eriksson, Eva; Bjerg, Poul L; Baun, Anders

    2010-11-25

    The use of nanoscaled zero-valent iron particles (nZVI) to remediate contaminated soil and groundwater has received increasing amounts of attention within the last decade, primarily due to its potential for broader application, higher reactivity, and cost-effectiveness compared to conventional zero-valent iron applications and other in situ methods. However, the potential environmental risks of nZVI in in situ field scale applications are largely unknown at the present and traditional environmental risk assessment approaches are not yet able to be completed. Therefore, it may not yet be fully clear how to consider the environmental benefits and risks of nZVI for in situ applications. This analysis therefore addresses the challenges of comprehensively considering and weighing the expected environmental benefits and potential risks of this emerging environmentally-beneficial nanotechnology, particularly relevant for environmental engineers, scientists, and decision makers. We find that most of the benefits of using nZVI are based on near-term considerations, and large data gaps currently exist within almost all aspects of environmental exposure and effect assessments. We also find that while a wide range of decision support tools and frameworks alternative to risk assessment are currently available, a thorough evaluation of these should be undertaken in the near future to assess their full relevancy for nZVI at specific sites. Due to the absence of data in environmental risk evaluations, we apply a 'best' and 'worst' case scenario evaluation as a first step to qualitatively evaluate the current state-of-knowledge regarding the potential environmental risks of nZVI. The result of this preliminary qualitative evaluation indicates that at present, there are no significant grounds on which to form the basis that nZVI currently poses a significant, apparent risk to the environment, although the majority of the most serious criteria (i.e. potential for persistency

  2. Stabilisation of nanoscale zero-valent iron with biochar for enhanced transport and in-situ remediation of hexavalent chromium in soil.

    PubMed

    Su, Huijie; Fang, Zhanqiang; Tsang, Pokeung Eric; Fang, Jianzhang; Zhao, Dongye

    2016-07-01

    In this study, a biochar-supported nanoscale zero-valent iron (nZVI@BC) material was used for in situ remediation of hexavalent chromium-contaminated soil. Sedimentation tests and column experiments were used to compare the stability and mobility of nZVI@BC and bare-nZVI. The immobilisation efficiency of chromium, toxic effect of chromium and the content of iron were assessed through leaching tests and pot experiments. Sedimentation tests and transport experiments indicated that nZVI@BC with nZVI to BC mass ratio of 1:1 exhibited better stability and mobility than that of bare-nZVI. The immobilisation efficiency of Cr(VI) and Crtotal was 100% and 92.9%, respectively, when the soil was treated with 8 g/kg of nZVI@BC for 15 days. Moreover, such remediation effectively reduced the leachability of Fe caused by bare-nZVI. In addition, pot experiments showed that such remediation reduced the phytotoxicity of Cr and the leachable Fe and was favourable for plant growth. PMID:27064615

  3. [Dynamic effects of commonly co-existing anions on the removal of selenite from groundwater by nanoscale zero-valent iron].

    PubMed

    Yang, Wen-Jun; Guo, Ying-Qing; Du, Er-Deng

    2014-05-01

    Batch experiments are used to research selenite removal from groundwater by nanoscale zero-valent iron (nZVI) , and dynamic effects of commonly co-existing anions on the removal of selenite are also investigated. The results showed that under anoxic conditions,when nZVI dose was 0.1 g.L-1 , the concentration of Se( IV)/sodium chloride was 100 micromol.L-1/0. 01 mol L-1 , pH = 7.0, T = 25 degrees C +/- 1 degrees C, auto-adding 1 mmol.L -1 CO(2-)(3) or SO(2-)(4) , 5 mg. L -1 humic acid (HA), the removals of Se( IV ) were obviously inhibited. The weak effect on the removal of Se( IV) was observed when added 0. 5 mmol L- Ca2+ or Mg2 ,while concentrations of Ca2+ and Mg2+ were 3 mmol L-1 and 3 mmol L-1 respectively, removal efficiency of Se( IV) were evidently decreased. Without coexisting ions, Se( IV) were totally removed in 20 min, while with co-existing ions, removal efficiency of Se( NV) were achieved 100% in 30 min. Bivalent iron tended to stationary with the remove of Se( WV) in reaction processes. ORP rapidly decreased from positive to negative in the process of reaction, which illustrated the process of remove Se( IV) by nZVI was the reduction reaction. PMID:25055668

  4. 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. PMID:26598990

  5. Effects of washing solution and drying condition on reactivity of nano-scale zero valent irons (nZVIs) synthesized by borohydride reduction.

    PubMed

    Woo, Heesoo; Park, Junboum; Lee, Seockheon; Lee, Seunghak

    2014-02-01

    Washing and drying processes are essential when synthesizing nano-scale zero valent irons (nZVIs) by borohydride reduction of iron salts in aqueous phase. However, effects of these processes on nZVI reactivity have not been investigated in detail, although different washing and drying conditions might alter surface characteristics of nZVIs and thus vary their reactivity towards reducible contaminants. In this study, effects of three washing solutions and drying conditions on the reactivity of nZVIs for nitrate were investigated. Washing with volatile solvents and drying under anaerobic condition decreased thickness of Fe-oxide layer on nZVIs and increased content of Fe(2+)-containing oxides in the layer, which enhanced nZVI reactivity toward nitrate. Volatile solvent washing could minimize the decrease in nZVI reactivity according to changing anaerobic drying condition to aerobic. Findings from this study suggest that application of washing with volatile solvents and drying under aerobic condition should be recommended as effective processes to obtain nZVIs with maximum reactivity at reasonable costs and efforts. PMID:24290304

  6. Conversion of mill-scale waste to nanoscale zero valent iron (nZVI) for 'green' hydrogen generation via metal-steam reforming

    NASA Astrophysics Data System (ADS)

    Kesavan, Sathees Kumar

    The Proton Exchange Membrane Fuel Cells (PEMFCs) are the most preferred and efficient energy conversion devices for automotive applications but demand high purity hydrogen which comes at a premium price. The currently pursued hydrogen generation methods suffer from issues such as, low efficiency, high cost, environmental non-benignity, and, in some cases, commercial non-viability. Many of these drawbacks including the CO contamination and, storage and delivery can be overcome by resorting to metal-steam reforming (MSR) using iron from steel industry's mill-scale waste. A novel solution-based room temperature technique using sodium borohydride (NaBH4) as the reducing agent has been developed that produces highly active nanoscale (30-40 nm) iron particles. A slightly modified version of this technique using a surfactant and water oil microemulsion resulted in the formation of 5 nm Fe particles. By using hydrazine (N2H4) as an inexpensive and more stable (compared to NaBH4) reductant, body centered cubic iron particles with edge dimensions ˜5 nm were obtained under mild solvothermal conditions in ethanol. The nanoscale zero valent iron (nZVI) powder showed improved kinetics and greater propensity for hydrogen generation than the coarser microscale iron obtained through traditional reduction techniques. To initiate and sustain the somewhat endothermic MSR process, a solar concentrator consisting of a convex polyacrylic sheet with aluminum reflective coating was fabricated. This unique combination of mill-scale waste as iron source, hydrazine as the reductant, mild process conditions for nZVI generation and solar energy as the impetus for actuating MSR, obviates several drawbacks plaguing the grand scheme of producing, storing and delivering pure and humidified H2 to a PEMFC stack.

  7. A Two and Half-Year-Performance Evaluation of a Field Test on Treatment of Source Zone Tetrachloroethene and Its Chlorinated Daughter Products Using Emulsified Zaro Valent Iron Nanoparticles

    EPA Science Inventory

    A field test of emulsified zero valent iron (EZVI) nanoparticles was conducted at Parris Island, SC, USA and was monitored for two and half years to assess the treatment of subsurface-source zone chlorinated volatile organic compounds (CVOCs) dominated by tetrachloroethene (PCE) ...

  8. Pilot-scale demonstration of the hybrid zero-valent iron process for treating flue-gas-desulfurization wastewater: part I.

    PubMed

    Huang, Yong H; Peddi, Phani K; Zeng, Hui; Tang, Ci-Lai; Teng, Xinjun

    2013-01-01

    The hybrid zero-valent-iron (hZVI) process is a novel chemical treatment process that has shown great potential in previous laboratory and field bench-top scale tests for removing selenium, mercury and nutrients from various industrial wastewaters. In this study, a pilot-scale demonstration was conducted to continuously treat 3.8-7.6 L/min (1-2 gpm) of the flue-gas-desulfurization (FGD) wastewater at a coal-fired power plant for five months. Results show that the hZVI process could simultaneously reduce selenate-Se from 1 to 3 mg/L to below 10 μg/L and mercury from over 100 μg/L to below 10 ng/L in compliance with the new stringent effluent discharge limits planned by the U.S. EPA for Se and Hg. A three-stage hZVI system with a combined hydraulic retention time of 12 h is sufficient for Se treatment, while a single-stage system can meet Hg treatment requirement. The successful pilot study demonstrated that the hZVI process is scalable and could be a reliable, low-cost, high-performance treatment platform with many application potentials, particularly, for solving some of the toughest heavy metal water problems. PMID:23128616

  9. Transport of sucrose-modified nanoscale zero-valent iron in saturated porous media: role of media size, injection rate and input concentration.

    PubMed

    Li, Hui; Zhao, Yong-sheng; Han, Zhan-tao; Hong, Mei

    2015-01-01

    The growing use of nanoscale zero-valent iron (NZVI) in the remediation of contaminated groundwater raises concerns regarding its transport in aquifers. Laboratory-scale sand-packed column experiments were conducted with bare and sucrose-modified NZVI (SM-NZVI) to improve our understanding of the transport of the nanoparticles in saturated porous media, as well as the role of media size, suspension injection rate and concentration on the nanoparticle behavior. As the main indicative parameters, the normalized effluent concentration was measured and the deposition rate coefficient (k) was calculated for different simulated conditions. Overall, compared to the high retention of bare NZVI in the saturated silica column, SM-NZVI suspension could travel through the coarse sand column easily. However, the transport of SM-NZVI particles was not very satisfactory in a smaller size granular matrix especially in fine silica sand. Furthermore, the value of k regularly decreased with the increasing injection rate of suspension but increased with suspension concentration, which could reflect the role of these factors in the SM-NZVI travel process. The calculation of k-value at the tests condition adequately described the experimental results from the point of deposition dynamics, which meant the assumption of first-order deposition kinetics for the transport of NZVI particles was reasonable and feasible. PMID:26524436

  10. Synthesis, physical properties and application of the zero-valent iron/titanium dioxide heterocomposite having high activity for the sustainable photocatalytic removal of hexavalent chromium in water.

    PubMed

    Petala, Eleni; Baikousi, Maria; Karakassides, Michael A; Zoppellaro, Giorgio; Filip, Jan; Tuček, Jiří; Vasilopoulos, Konstantinos C; Pechoušek, Jiří; Zbořil, Radek

    2016-04-21

    A magnetic photocatalytic material composed of nanoscale zero-valent iron (nZVI) homogeneously distributed over a mesoporous nanocrystalline TiO2 matrix has been prepared by a multistage chemical process, including sol-gel technique, wet impregnation, and chemical reduction. X-ray powder diffraction and Raman spectroscopy were used for the structural and chemical characterization of the magnetic photocatalyst, while bulk magnetization measurements and scanning/transmission electron microscopy were employed to determine the physical and textural properties of the photocatalyst. The synthesized nZVI@TiO2 photocatalyst shows very high efficiency in the removal of hexavalent chromium, Cr(vi), from water. The degradation rate follows a pseudo-first-order kinetic model. Most importantly, the remarkable efficiency of the photocatalyst is found to be due to the synergistic contributions of both counterparts, nZVI and TiO2, as validated by comparative experiments with neat TiO2 and nZVI@TiO2 under UV-C irradiation and without irradiation. New insights into the mechanism of synergistic degradation of chromium(vi) and suppressed oxidation of nZVI particles in the composite material are proposed and therein discussed. PMID:27035846

  11. The use of the core-shell structure of zero-valent iron nanoparticles (NZVI) for long-term removal of sulphide in sludge during anaerobic digestion.

    PubMed

    Su, Lianghu; Zhen, Guangyin; Zhang, Longjiang; Zhao, Youcai; Niu, Dongjie; Chai, Xiaoli

    2015-12-01

    A core-shell structure results in zero-valent iron nanoparticles (NZVI) with manifold functional properties. In this study, the long-term effects of NZVI on hydrogen sulphide removal in an anaerobic sludge digester were investigated. Within 20 days, the average hydrogen sulphide content in the biogas was successfully reduced from 300 (or 3620 of sulphate-rich sludge) mg Nm(-3) to 6.1 (121), 0.9 (3.3) and 0.5 (1.3) mg Nm(-3) in the presence of 0.05, 0.10 and 0.20% (wt) NZVI, respectively. Methane yield was enhanced at the low NZVI dose (0.05-0.10%) but decreased at the elevated dose (0.20%). Methane production and volatile solid degradation analyses implied that doses of 0.5-0.10% NZVI could accelerate sludge stabilization during anaerobic digestion. The phosphorus fractionation profile suggested that methane production could be inhibited at the elevated NZVI dose, partly due to the limited availability of soluble phosphorus due to the immobilization of bioavailable-P through the formation of vivianite. An analysis of the reducible inorganic sulphur species revealed that the elimination of hydrogen sulphide occurred via the reaction between hydrogen sulphide and the oxide shell of NZVI, which mainly formed FeS and some FeS2 and S(0). PMID:26565792

  12. Boron nitride nanoplates supported zero-valent iron nanocomposites for enhanced decolorization of methyl orange with the assistance of ultrasonic irradiation.

    PubMed

    Zha, Yiming; Wang, Tianlin

    2016-01-01

    In this work, boron nitride nanoplates (BNNPs) supported nanoscale zero-valent iron (nZVI) was prepared through facile liquid-phase chemical reduction of ferric ion by borohydride under ambient conditions in the presence of BNNPs. The nZVI@BNNPs hybrids were characterized by scanning electron microscopy, X-ray diffraction and magnetic properties measurement. The hybrid material was evaluated for decolorization of a common azo dye, methyl orange (MO), with the assistance of ultrasonic irradiation. Results exhibited that a complete decolorization of 100 mg/L MO was achieved within 6 min using nZVI@BNNPs as the active material. Compared with bare nZVI and BNNPs, nZVI@BNNPs provided a faster reaction process for MO decolorization. The kinetic rate constants of MO decolorization reached 0.8175 min(-1) under ultrasound-assisted condition due to the synergistic effect of ultrasonic irradiation. Fluorescence spectrum experiment confirmed that hydroxyl radicals could be generated in the system combined nZVI with ultrasonic irradiation, and as a result, hydroxyl radicals would contribute to the decolorization process of MO. PMID:26819388

  13. Determination of rate constants and branching ratios for TCE degradation by zero-valent iron using a chain decay multispecies model

    NASA Astrophysics Data System (ADS)

    Hwang, Hyoun-Tae; Jeen, Sung-Wook; Sudicky, Edward A.; Illman, Walter A.

    2015-06-01

    The applicability of a newly-developed chain-decay multispecies model (CMM) was validated by obtaining kinetic rate constants and branching ratios along the reaction pathways of trichloroethene (TCE) reduction by zero-valent iron (ZVI) from column experiments. Changes in rate constants and branching ratios for individual reactions for degradation products over time for two columns under different geochemical conditions were examined to provide ranges of those parameters expected over the long-term. As compared to the column receiving deionized water, the column receiving dissolved CaCO3 showed higher mean degradation rates for TCE and all of its degradation products. However, the column experienced faster reactivity loss toward TCE degradation due to precipitation of secondary carbonate minerals, as indicated by a higher value for the ratio of maximum to minimum TCE degradation rate observed over time. From the calculated branching ratios, it was found that TCE and cis-dichloroethene (cis-DCE) were dominantly dechlorinated to chloroacetylene and acetylene, respectively, through reductive elimination for both columns. The CMM model, validated by the column test data in this study, provides a convenient tool to determine simultaneously the critical design parameters for permeable reactive barriers and natural attenuation such as rate constants and branching ratios.

  14. Investigation of heavy metal (Cu, Pb, Cd, and Cr) stabilization in river sediment by nano-zero-valent iron/activated carbon composite.

    PubMed

    Chen, Wei-fang; Zhang, Jinghui; Zhang, Xiaomao; Wang, Weiya; Li, Yuxiang

    2016-01-01

    Nano-zero-valent iron/activated carbon (nZVI/AC) composite was evaluated for its effectiveness in the stabilization of Cu, Pb, Cd, and Cr in dredged river sediment. Synthetic precipitation leaching procedure (SPLP) and toxicity characteristic leaching procedure (TCLP) were adopted to compare the effects of nZVI/AC dosage, particle size, time duration, and temperature on heavy metal leachability. The results show that leachability dropped considerably with the addition of nZVI/AC and powdered particles in the size of 0.075-0.18 mm was more effective in stabilization than granular ones. Stabilization effect was stable in long-term and robust against changes in temperature. Tessier sequential extraction revealed that heavy metals were associated with solid particle, inorganic or organic matters in sediment. The addition of nZVI/AC was able to convert relatively weakly bound heavy metals into more strongly bound species and thus reduce the bioavailability and toxicity. Also, the standard potential of heavy metals may decide the mechanism of stabilization process. PMID:26370818

  15. Stability and pH-independence of nano-zero-valent iron intercalated montmorillonite and its application on Cr(VI) removal.

    PubMed

    Wu, Limei; Liao, Libing; Lv, Guocheng; Qin, Faxiang

    2015-08-01

    Composite of nano-zero-valent iron and montmorillonite (NZVI/MMT) was prepared by inserting NZVI into the interlayer of montmorillonite. The unique structure montmorillonite with isolated exchangeable Fe(III) cations residing near the sites of structural negative charges inhibited the agglomeration of ZVI and result in the formation of ZVI particles in the montmorillonite interlayer regions. NZVI/MMT was demonstrated to possess large specific surface area and outstanding reducibility that encourage rapid and stable reaction with Cr (VI). Besides, the intercalation also makes NZVI well dispersed and more stable in the interlayer, thereby improving the reaction capacity by 16 times. The effects of pH value, initial concentration of Cr (VI) and reaction time on Cr (VI) removal have also been investigated in detail. According to PXRD and XPS characterization, NZVI/Cr (VI) redox reaction occurred in the interlayer of MMT. The study of NZVI/MMT is instrumental to the development of remediation technologies for persistent environmental contaminants. PMID:26011800

  16. Degradation of 2,4,6-Trichlorophenol Using Hydrogen Peroxide Catalyzed by Nanoscale Zero-Valent Iron Supported on Ion Exchange Resin.

    PubMed

    Tai, Chao; She, Jiaping; Yin, Yongguang; Zhao, Tongqian; Wu, Li

    2016-06-01

    Nanoscale zero-valent iron (NZVI) supported on ion exchange resin was prepared and characterized by scanning electron microscope and energy dispersive spectroscopy, with a simple model developed for describing the catalyst. The degradation of 2,4,6-trichlorophenol (2,4,6-TCP) by hydrogen peroxide using NZVI supported on ion exchange resin as the catalyst, was studied. The results showed that 2,4,6-TCP with a concentration of 1 mmol L(-1) could be well degraded into low molecule weight organic acids in two hours. The optimized condition was as follows: pH, 3.0; temperature, 35 degrees C; catalyst dosage, 1.5 g; and hydrogen peroxide, 0.16 mmol L(-1). The catalyst has good reusability, with no catalytic efficiency decreasing even after ten times recycles. A possible mechanism of 2,4,6-TCP degradation was proposed, based on the products indentified by GC-MS after derived using trimethylsulfonium hydroxide. PMID:27427643

  17. Carbothermal synthesis of ordered mesoporous carbon-supported nano zero-valent iron with enhanced stability and activity for hexavalent chromium reduction.

    PubMed

    Dai, Ying; Hu, Yuchen; Jiang, Baojiang; Zou, Jinlong; Tian, Guohui; Fu, Honggang

    2016-05-15

    Composites of nano zero-valent iron (nZVI) and ordered mesoporous carbon (OMC) are prepared by using simultaneous carbothermal reduction methods. The reactivity and stability of nZVI are expected to be enhanced by embedding it in the ordered pore channels. The structure characteristics of nZVI/OMC and the removal pathway for hexavalent chromium (Cr(VI)) by nZVI/OMC are investigated. Results show that nZVI/OMC with a surface area of 715.16 m(2) g(-1) is obtained at 900 °C. nZVI with particle sizes of 20-30 nm is uniformly embedded in the OMC skeleton. The stability of nZVI is enhanced by surrounding it with a broad carbon layer and a little γ-Fe is derived from the passivation of α-Fe. Detection of ferric state (Fe 2p3/2, around 711.2eV) species confirms that part of the nZVI on the outer surface is inevitably oxidized by O2, even when unused. The removal efficiency of Cr(VI) (50 mg L(-1)) by nZVI/OMC is near 99% within 10 min through reduction (dominant mechanism) and adsorption. nZVI/OMC has the advantage in removal efficiency and reusability in comparison to nZVI/C, OMC and nZVI. This study suggests that nZVI/OMC has the potential for remediation of heavy metal pollution in water. PMID:25898797

  18. Examination of Cr(VI) treatment by zero-valent iron using in situ, real-time X-ray absorption spectroscopy and Cr isotope measurements

    NASA Astrophysics Data System (ADS)

    Jamieson-Hanes, Julia H.; Lentz, Adam M.; Amos, Richard T.; Ptacek, Carol J.; Blowes, David W.

    2014-10-01

    A series of replicate flow-through cell experiments was conducted to characterize Cr isotope fractionation during Cr(VI) treatment by granular zero-valent iron (ZVI). Synthetic groundwater containing 50 mg L-1 Cr(VI) was pumped upward through a custom-made cell packed with ZVI under anaerobic conditions. The geochemical evolution of the system was monitored using pH and redox measurements, while aqueous effluent samples were retained for analysis of cations and Cr isotopes. Real-time, in situ X-ray absorption near edge structure (XANES) spectroscopy collected via a Kapton® window in the cell provided additional information on the speciation of the reaction products. Increases in δ53Cr values corresponding to decreases in Cr(VI) concentration suggested the occurrence of redox processes. Spectroscopic results correlated well with the isotope data, indicating reduction of Cr(VI) to Cr(III). The isotope data did not appear to follow a single trend. A two-stage system was proposed to explain the complex isotope trend, where the rapid Cr removal was associated with very little fractionation (ε = -0.2‰), whereas slower removal was associated with a greater degree of fractionation (ε = -1.2‰ to -1.5‰). Reactive transport modeling was used to quantify distinct isotope fractionation values (ε), differentiated by a significant change in the Cr removal rate.

  19. Molecular Stress Responses to Nano-Sized Zero-Valent Iron (nZVI) Particles in the Soil Bacterium Pseudomonas stutzeri

    PubMed Central

    Saccà, Maria Ludovica; Fajardo, Carmen; Martinez-Gomariz, Montserrat; Costa, Gonzalo; Nande, Mar; Martin, Margarita

    2014-01-01

    Nanotoxicological studies were performed in vitro using the common soil bacterium Pseudomonas stutzeri to assess the potentially toxic impact of commercial nano-sized zero-valent iron (nZVI) particles, which are currently used for environmental remediation projects. The phenotypic response of P. stutzeri to nZVI toxicity includes an initial insult to the cell wall, as evidenced by TEM micrographs. Transcriptional analyses using genes of particular relevance in cellular activity revealed that no significant changes occurred among the relative expression ratios of narG, nirS, pykA or gyrA following nZVI exposure; however, a significant increase in katB expression was indicative of nZVI-induced oxidative stress in P. stutzeri. A proteomic approach identified two major defence mechanisms that occurred in response to nZVI exposure: a downregulation of membrane proteins and an upregulation of proteins involved in reducing intracellular oxidative stress. These biomarkers served as early indicators of nZVI response in this soil bacterium, and may provide relevant information for environmental hazard assessment. PMID:24586957

  20. A review of the environmental implications of in situ remediation by nanoscale zero valent iron (nZVI): Behavior, transport and impacts on microbial communities.

    PubMed

    Lefevre, Emilie; Bossa, Nathan; Wiesner, Mark R; Gunsch, Claudia K

    2016-09-15

    The increasing use of strategies incorporating nanoscale zero valent iron (nZVI) for soil and groundwater in situ remediation is raising some concerns regarding the potential adverse effects nZVI could have on indigenous microbial communities and ecosystem functioning. This review provides an overview of the current literature pertaining to the impacts of nZVI applications on microbial communities. Toxicity studies suggest that cell membrane disruption and oxidative stress through the generation of Fe(2+) and reactive oxygen species by nZVI are the main mechanisms contributing to nZVI cytotoxicity. In addition, nZVI has been shown to substantially alter the taxonomic and functional composition of indigenous microbial communities. However, because the physico-chemical conditions encountered in situ highly modulate nZVI toxicity, a better understanding of the environmental factors affecting nZVI toxicity and transport in the environment is of primary importance in evaluating the ecological consequences that could result from a more extensive use of nZVI. PMID:26897610

  1. Interaction between Cu2+ and different types of surface-modified nanoscale zero-valent iron during their transport in porous media.

    PubMed

    Dong, Haoran; Zeng, Guangming; Zhang, Chang; Liang, Jie; Ahmad, Kito; Xu, Piao; He, Xiaoxiao; Lai, Mingyong

    2015-06-01

    This study investigated the interaction between Cu2+ and nano zero-valent iron (NZVI) coated with three types of stabilizers (i.e., polyacrylic acid [PAA], Tween-20 and starch) by examining the Cu2+ uptake, colloidal stability and mobility of surface-modified NZVI (SM-NZVI) in the presence of Cu2+. The uptake of Cu2+ by SM-NZVI and the colloidal stability of the Cu-bearing SM-NZVI were examined in batch tests. The results showed that NZVI coated with different modifiers exhibited different affinities for Cu2+, which resulted in varying colloidal stability of different SM-NZVI in the presence of Cu2+. The presence of Cu2+ exerted a slight influence on the aggregation and settling of NZVI modified with PAA or Tween-20. However, the presence of Cu2+ caused significant aggregation and sedimentation of starch-modified NZVI, which is due to Cu2+ complexation with the starch molecules coated on the surface of the particles. Column experiments were conducted to investigate the co-transport of Cu2+ in association with SM-NZVI in water-saturated quartz sand. It was presumed that a physical straining mechanism accounted for the retention of Cu-bearing SM-NZVI in the porous media. Moreover, the enhanced aggregation of SM-NZVI in the presence of Cu2+ may be contributing to this straining effect. PMID:26040744

  2. Pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater using a combined zero-valent iron (ZVI) reduction and Fenton oxidation process.

    PubMed

    Shen, Jinyou; Ou, Changjin; Zhou, Zongyuan; Chen, Jun; Fang, Kexiong; Sun, Xiuyun; Li, Jiansheng; Zhou, Lin; Wang, Lianjun

    2013-09-15

    A combined zero-valent iron (ZVI) reduction and Fenton oxidation process was tested for the pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater. Operating conditions were optimized and overall performance of the combined process was evaluated. For ZVI process, almost complete reduction of nitroaromatic compounds was observed at empty bed contact time (EBCT) of 8h. For Fenton process, the optimal pH, H₂O₂ to Fe(II) molar ratio, H₂O₂ dosage and hydraulic retention time (HRT) were found to be 3.0, 15, 0.216 mol/L and 5h, respectively. After pretreatment by the combined ZVI-Fenton process under the optimal conditions, aromatic organic compound removal was as high as 77.2%, while the majority of COD remained to be further treated by sequent biological process. The combined anaerobic-aerobic process consisted of an anaerobic baffled reactor (ABR) and a moving-bed biofilm reactor (MBBR) was operated for 3 months, fed with ZVI-Fenton effluent. The results revealed that the coupled ZVI-Fenton-ABR-MBBR system was significantly efficient in terms of correcting the effluent's main parameters of relevance, mainly aromatic compounds concentration, COD concentration, color and acute toxicity. These results indicate that the combined ZVI-Fenton process offers bright prospects for the pretreatment of wastewater containing nitroaromatic compounds. PMID:23892166

  3. The enhancement effect of pre-reduction using zero-valent iron on the solidification of chromite ore processing residue by blast furnace slag and calcium hydroxide.

    PubMed

    Li, Jinchunzi; Chen, Zhonglin; Shen, Jimin; Wang, Binyuan; Fan, Leitao

    2015-09-01

    A bench scale study was performed to assess the effectiveness of the solidification of chromite ore processing residue (COPR) by blast furnace slag and calcium hydroxide, and investigate the enhancement effect of pre-reduction using zero-valent iron (ZVI) on the solidification treatment. The degree of Cr immobilization was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) as well as the solid waste-extraction procedure for leaching toxicity-sulfuric acid & nitric acid method (Chinese standard HJ/T299-2007). Strength tests and semi-dynamic leaching tests were implemented to investigate the potential for reusing the final treatment product as a readily available construction material. The experimental results showed that the performance of pre-reduction/solidification (S/S) was superior to that of solidification alone. After pre-reduction, all of the S/S treated COPR samples met the TCLP limit for total Cr (5 mg L(-1)), whereas the samples with a COPR content below 40% met the pollution control limit of bricks and building block products (Chinese standard HJ/T 301-2007) produced with COPR for total Cr (0.3 mg L(-1)). At the same time, all of the S/S treated specimens tested were suitable for utilization at certain levels. PMID:25929874

  4. Enhanced sequestration of Cr(VI) by nanoscale zero-valent iron supported on layered double hydroxide by batch and XAFS study.

    PubMed

    Sheng, Guodong; Hu, Jun; Li, Hui; Li, Jiaxing; Huang, Yuying

    2016-04-01

    Herein, the reduction of nanoscale zero-valent iron (NZVI) and adsorption of layered double hydroxides (LDH) to sequester Cr(VI) were well combined by the immobilization of NZVI onto LDH surface (NZVI/LDH). The characterization results revealed that LDH decreased NZVI aggregation and thus increased Cr(VI) sequestration. The batch results indicated that Cr(VI) sequestration by NZVI/LDH was higher than that of NZVI, and superior to the sum of reduction and adsorption. The LDH with good anion exchange property allowed the adsorption of Cr(VI), facilitating interfacial reaction by increasing the local concentration of Cr(VI) in the NZVI vicinity. X-ray absorption near edge structure (XANES) results indicated that Cr(VI) was almost completely reduced to Cr(III) by NZVI/LDH, but Cr(VI) was partly reduced to Cr(III) by NZVI with a trace of Cr(VI) adsorbed on corrosion products. The coordination environment of Cr from extended X-ray absorption fine structure (EXAFS) analysis revealed that LDH could be a good scavenger for the insoluble products produced during reaction. So, the insoluble products on NZVI could be reduced, and its reactivity could be maintained. These results demonstrated that NZVI/LDH exhibits multiple functionalities relevant to the remediation of Cr(VI)-contaminated sites. PMID:26807943

  5. [Solidification/Stabilization of Chromite Ore Processing Residue (COPR) Using Zero-Valent Iron and Lime-Activated Ground Granulated Blast Furnace Slag].

    PubMed

    Chen, Zhong-lin; Li, Jin-chunzi; Wang, Bin-yuan; Fan, Lei-tao; Shen, Ji-min

    2015-08-01

    The solidification/stabilization (S/S) of chromite ore processing residue (COPR) was performed using zero-valent iron (ZVI) and lime-activated ground granulated blast furnace slag (GGBFS). The degree of Cr immobilization was evaluated using the leaching procedure, mineral composition analysis and morphology analysis. Semi-dynamic leaching tests were implemented to investigate the potential for reusing the final treatment product as a readily available construction material. The results showed that after reduction, all of the S/S treated COPR samples met the pollution control limit of bricks and building block products (Chinese standard HJ/T 301-2007) produced with COPR for total Cr (0.3 mg x L(-1)), the compressive strength of all the S/S samples could meet the compressive strength standard (15 MPa) for producing clay bricks, and Cr existed as the specie that bound to Fe/Mn oxides in the S/S samples. At the same time, all of the S/S treated specimens tested were suitable for utilization at certain levels. PMID:26592036

  6. SBA-15-incorporated nanoscale zero-valent iron particles for chromium(VI) removal from groundwater: mechanism, effect of pH, humic acid and sustained reactivity.

    PubMed

    Sun, Xia; Yan, Yubo; Li, Jiansheng; Han, Weiqing; Wang, Lianjun

    2014-02-15

    Nanoscale zero-valent iron particles (NZVIs) were incorporated inside the channels of SBA-15 rods by a "two solvents" reduction technique and used to remove Cr(VI) from groundwater. The resulting NZVIs/SBA-15 composites before and after reaction were characterized by N2 adsorption/desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Results helped to propose the mechanism of Cr(VI) removal by NZVIs/SBA-15, where Cr(VI) in aqueous was firstly impregnated into the channels of the silica, then adsorbed on the surfaces of the incorporated NZVIs and reduced to Cr(III) directly in the inner pores of the silica. Corrosion products included Fe2O3, FeO(OH), Fe3O4 and Cr2FeO4. Batch experiments revealed that Cr(VI) removal decreased from 99.7% to 92.8% when the initial solution pH increased from 5.5 to 9.0, accompanied by the decrease of the kobs from 0.600 to 0.024 min(-1). Humic acid (HA) had a little effect on the removal efficiency of Cr(VI) by NZVIs/SBA-15 but could decrease the reduction rate. The stable reduction of NZVIs/SBA-15 was observed within six cycles. NZVIs/SBA-15 composites offer a promising alternative material to remove heavy metals from groundwater. PMID:24374562

  7. Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite.

    PubMed

    Fu, Jie; Xu, Zhen; Li, Qing-Shan; Chen, Song; An, Shu-Qing; Zeng, Qing-Fu; Zhu, Hai-Liang

    2010-01-01

    A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon (ZVI/AC), microwave discharge electrodeless lamp/sodium hypochlorite (MDEL/NaClO) and the combination of ZVI/AC-MDEL/NaClO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaClO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaClO, we found that in the ZVI/AC-MEDL/NaClO process, ZVI/AC could break the azo bond firstly and then MEDL/NaClO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency. PMID:20617726

  8. Treatment of aqueous bisphenol A using nano-sized zero-valent iron in the presence of hydrogen peroxide and persulfate oxidants.

    PubMed

    Girit, B; Dursun, D; Olmez-Hanci, T; Arslan-Alaton, I

    2015-01-01

    Bisphenol A (BPA) is an industrial pollutant considered as one of the major endocrine-disrupting chemicals found in natural waters. In the present study, the use of a commercial, air-stable, zero-valent iron (ZVI) powder, consisting of Fe0 surface stabilized nanoparticles was examined for the treatment of 20 mg/L, aqueous BPA solutions. The influence of pH (3, 5, 7), addition of hydrogen peroxide (HP) and persulfate (PS) oxidants (0.0, 1.25 and 2.5 mM) as well as temperature (25 and 50 °C) was studied for BPA treatment with 1 g/L ZVI. ZVI coupled with HP or PS provided an effective treatment system, which was based on rapid ZVI-mediated decomposition of the above-mentioned oxidants, resulting in complete BPA as well as significant total organic carbon (TOC) (88%) removals, in particular when PS was employed as the oxidant. Increasing the PS concentration and reaction temperature dramatically enhanced PS decomposition and BPA removal rates, whereas HP was not very effective in TOC removals and at elevated temperatures. According to the bioassays conducted with Vibrio fischeri and Pseudokirchneriella subcapitata, the acute toxicity of aqueous BPA fluctuated at first but decreased appreciably at the end of ZVI/PS treatment. PMID:26067507

  9. Simultaneous removal of Cr(VI) and phenol by persulfate activated with bentonite-supported nanoscale zero-valent iron: Reactivity and mechanism.

    PubMed

    Diao, Zeng-Hui; Xu, Xiang-Rong; Chen, Hui; Jiang, Dan; Yang, Yu-Xi; Kong, Ling-Jun; Sun, Yu-Xin; Hu, Yong-Xia; Hao, Qin-Wei; Liu, Ling

    2016-10-01

    The applicability of bentonite-supported nanoscale zero-valent iron (B-nZVI) as a catalyst to activate persulfate (PS) for the simultaneous removal of Cr(VI) and phenol was systematically investigated in this study. Experimental results demonstrated that phenol degradation was significantly enhanced under acidic condition and with oxygen supply, whereas the Cr(VI) reduction was not obviously declined. The removal efficiencies of Cr(VI) and phenol in B-nZVI/PS combined system were 99.8 and 72.3%, respectively. Cr(VI) reduction and phenol oxidation was simultaneously achieved in B-nZVI/PS combined system, which provided a promising environmental treatment for industrial wastewater containing metal ions and organic compounds. An acidic condition was more favorable to the decomposition of persulfate for the production of sulfate radicals. Radical scavenging tests revealed that the predominant reactive oxygen species for phenol degradation was SO4(-), neither HO nor O2(-). A reaction mechanism, which involves the Cr(VI) removal mainly by the reduction of nZVI and the degradation of phenol mainly by the SO4(-) from the decomposition of persulfate, was proposed. These findings revealed that B-nZVI/PS combined system has a potential in the environmental remediation polluted jointly by organic compounds and/or heavy metals. PMID:27235826

  10. 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

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

    SciTech Connect

    Jin, Xiaoying; Chen, Zhengxian; Zhou, Rongbing; Chen, Zuliang

    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 of 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.

  12. Zero-valent iron/iron oxide-oxyhydroxide/graphene as a magnetic sorbent for the enrichment of polychlorinated biphenyls, polyaromatic hydrocarbons and phthalates prior to gas chromatography-mass spectrometry.

    PubMed

    Karamani, Anna A; Douvalis, Alexios P; Stalikas, Constantine D

    2013-01-01

    A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe(0)/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications. PMID:23228921

  13. [Effects of particle size of zero-valent iron on the reactivity of activating persulfate and kinetics for the degradation of acid orange 7].

    PubMed

    Li, Huan-xuan; Wan, Jin-quan; Ma, Yong-wen; Huang, Ming-zhiz; Wang, Yan; Chen Yang, Mei

    2014-09-01

    This research described the heterogeneous reactions of persulfate with different particle sizes of zero-valent iron (including 1 mm-ZVI,150 μm-ZVI,50 nm-ZVI) for degradation of acid orange 7(AO7) , and studied the kinetics and intermediate products of AO7 under these systems. The results demonstrated that these three types of ZVI were efficient in promoting the degradation of AO7, the degradation efficiencies of AO7 were 43% , 97% , and 100% within 90 min respectively, in the 1 mm-ZVI,150 μm-ZVI and 50 nm- ZVI systems, respectively. With the results of kinetic fitting models, the pseudo first-order kinetics exhibited better fitting results in the 1 mm-ZVI,150 μm-ZVI systems, while the second-order kinetics exhibited better fitting results in the 50 nm-ZVI system. And the different ZVI types exhibited difference on the AO7 degradation rate constant, which ranged as 50 nm-ZVI > 150 μm-ZVI > 1 mm-ZVI. The iron corrosion products coating on the ZVI after reaction were composed of α-Fe2 O3 and some Fe3O4 in the 1 mm-ZVI system while that consisted of Fe3O4 and α-Fe2O3, FeOOH respectively, in thel50 μm-ZVI and 50 nm-ZVI systems,. Which were identified by scanning electron microscope (SEM) with energy dispersive spectrometer (EDS) and Raman spectroscopy. Some intermediate products, including 2-naphthalenol, 2-methylphenol, 4-ethyl- 3-methyl-phenol, isoindole- 1,3-dione and phthalic acid et al. were identified by GC/MS measurement. Both UV-vis absorbance spectra and GC/MS determination indicated that there was difference in degradation paths of AO7 between the three systems. PMID:25518660

  14. Potential artifacts in interpretation of differential breakthrough of colloids and dissolved tracers in the context of transport in a zero-valent iron permeable reactive barrier.

    PubMed

    Zhang, B P; Johnson, W P; Piana, M J; Fuller, C C; Naftz, D L

    2001-01-01

    Many published studies have used visual comparison of the timing of peak breakthrough of colloids versus conservative dissolved tracers (hereafter referred to as dissolved tracers or tracers) in subsurface media to determine whether they are advected differently, and to elucidate the mechanisms of differential advection. This purely visual approach of determining differential advection may have artifacts, however, due to the attachment of colloids to subsurface media. The attachment of colloids to subsurface media may shift the colloidal peak breakthrough to earlier times, causing an apparent "faster" peak breakthrough of colloids relative to dissolve tracers even though the transport velocities for the colloids and the dissolved tracers may actually be equivalent. In this paper, a peak shift analysis was presented to illustrate the artifacts associated with the purely visual approach in determining differential advection, and to quantify the peak shift due to colloid attachment. This peak shift analysis was described within the context of microsphere and bromide transport within a zero-valent iron (ZVI) permeable reactive barrier (PRB) located in Fry Canyon, Utah. Application of the peak shift analysis to the field microsphere and bromide breakthrough data indicated that differential advection of the microspheres relative to the bromide occurred in the monitoring wells closest to the injection well in the PRB. It was hypothesized that the physical heterogeneity at the grain scale, presumably arising from differences in inter- versus intra-particle porosity, contributed to the differential advection of the microspheres versus the bromide in the PRB. The relative breakthrough (RB) of microspheres at different wells was inversely related to the ionic strength of ground water at these wells, in agreement with numerous studies showing that colloid attachment is directly related to solution ionic strength. PMID:11708449

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

    PubMed

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

    2013-06-01

    Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu(2+) and Zn(2+) from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu(2+) and Zn(2+) from a aqueous solution containing a 100 mg/l of Cu(2+) and Zn(2+), where 92.9 % Cu(2+) and 58.3 % Zn(2+) were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu(2+) and Zn(2+). A kinetics study indicated that removing Cu(2+) and Zn(2+) with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu(2+)and Zn(2+) on bentonite and the degradation of Cu(2+)and Zn(2+) by nZVI on the bentonite. However, Cu(2+) removal by B-nZVI was reduced rather than adsorption, while Zn(2+) removal was main adsorption. Finally, Cu(2+), Zn(2+), Ni(2+), Pb(2+) and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters. PMID:23114838

  16. Exploring the Role of Nanoscale Zero Valent Iron and Bacteria on the Degradation of a Multi-component Chlorinated Solvent at the Field Scale

    NASA Astrophysics Data System (ADS)

    Kocur, C. M.; Lomheim, L.; Boparai, H.; Chowdhury, A. I.; Weber, K.; Austrins, L. M.; Sleep, B. E.; Edwards, E.; O'Carroll, D. M.

    2013-12-01

    Nanoscale zero valent iron (nZVI) has advanced as a technology for the remediation of priority source zone contaminants in response to early laboratory studies that showed rapid rates of compound degradation. The challenges associated with the delivery of nZVI particles (eg. rapid aggregation and settling) were partially resolved with the addition of a polyelectrolyte polymers, like Carboxymethyl cellulose, that significantly improves the colloidal stability of particles allowing for more controlled injection and transport in the subsurface. Following nZVI application and abiotic contaminant degradation nZVI oxidizes and yields reducing conditions. These reducing conditions are ideal for many dechlorinating bacteria. Given this, application of nZVI for abiotic contaminant degradation followed by bioremediation has become an area of active research interest. In this study nZVI was injected into a contaminated sandy subsurface area. Concentrations of a range of chlorinated compounds, including chlorinated ethenes, ethanes, and methanes were monitored in detail following nano-particle injection in order to access short term abiotic degradation. Monitoring continued over a 2 year period to evaluate the long term effects of nZVI injection on the bacterial communities and the biotic degradation of targeted chlorinated compounds. The study focusses on the degradation and evolution of intermediate compounds from reaction with targeted contaminant compounds along the nZVI flow path. Bacterial populations were quantified before injection to confirm that beneficial chloride reducing bacteria were present on site. The microbiological response to the injection of nZVI was studied and the performance of bacteria along the nZVI flow path and outside the nZVI affected area will be compared.

  17. Potential artifacts in interpretation of differential breakthrough of colloids and dissolved tracers in the context of transport in a zero-valent iron permeable reactive barrier

    USGS Publications Warehouse

    Zhang, P.; Johnson, W.P.; Piana, M.J.; Fuller, C.C.; Naftz, D.L.

    2001-01-01

    Many published studies have used visual comparison of the timing of peak breakthrough of colloids versus conservative dissolved tracers (hereafter referred to as dissolved tracers or tracers) in subsurface media to determine whether they are advected differently, and to elucidate the mechanisms of differential advection. This purely visual approach of determining differential advection may have artifacts, however, due to the attachment of colloids to subsurface media. The attachment of colloids to subsurface media may shift the colloidal peak breakthrough to earlier times, causing an apparent "faster" peak breakthrough of colloids relative to dissolve tracers even though the transport velocities for the colloids and the dissolved tracers may actually be equivalent. In this paper, a peak shift analysis was presented to illustrate the artifacts associated with the purely visual approach in determining differential advection, and to quantify the peak shift due to colloid attachment. This peak shift analysis was described within the context of microsphere and bromide transport within a zero-valent iron (ZVI) permeable reactive barrier (PRB) located in Fry Canyon, Utah. Application of the peak shift analysis to the field microsphere and bromide breakthrough data indicated that differential advection of the microspheres relative to the bromide occurred in the monitoring wells closest to the injection well in the PRB. It was hypothesized that the physical heterogeneity at the grain scale, presumably arising from differences in inter- versus intra-particle porosity, contributed to the differential advection of the microspheres versus the bromide in the PRB. The relative breakthrough (RB) of microspheres at different wells was inversely related to the ionic strength of ground water at these wells, in agreement with numerous studies showing that colloid attachment is directly related to solution ionic strength.

  18. Reduction and immobilization of radionuclides and toxic metal ions using combined zero valent iron and anaerobic bacteria. 1998 annual progress report

    SciTech Connect

    Weathers, L.

    1998-06-01

    'Previous research findings indicate that both zero valent iron and sulfate reducing bacteria (SRB) can yield significant decreases in Cr(VI) or U(VI) concentrations due to abiotic and microbial reduction, respectively. The major hypothesis associated with this research project is that a combined abiotic-biological system can synergistically combine both processes to maximize metal ion reduction in an engineered permeable reactive barrier. The overall goal of this project is to design a combined abiotic/microbial, reactive, permeable, in-situ barrier with sufficient reductive potential to prevent downgradient migration of toxic metal ions. The field-scale application of this technology would utilize anaerobic digester sludge, Fe(O) particles for supporting anaerobic biofilms, and suitable aquifer material for construction of the barrier. Successful completion of this goal requires testing of the two hypotheses listed above by evaluating: (1) the rates of abiotic metal ion reduction, and (2) the rates of microbial metal ion reduction in microbial and combined abiotic/microbial reduction systems under a range of environmental conditions. This report summarizes work after one and one-half years of a three year project. Abiotic studies: The thrust of the abiotic research conducted to date has been to determine the rates of Cr(VI) reduction in batch reactors and to evaluate the role of aquifer materials on those rates. Experiments have been conducted to determine the rates of reduction by Fe(II) and Fe(O). The parameters that have been evaluated are the effect of pH and the presence of sulfide and aquifer material.'

  19. Influence of calcium ions on the colloidal stability of surface-modified nano zero-valent iron in the absence or presence of humic acid.

    PubMed

    Dong, Haoran; Lo, Irene M C

    2013-05-01

    To decrease aggregation and enhance the mobility of nano zero-valent iron (NZVI) used for in-situ groundwater remediation, the surface of such NZVI must be modified using organic stabilizers, which can provide electrostatic repulsion, and steric or electrosteric stabilization. However, the stability of the nanoparticles can also be affected by groundwater components such as cations and humic acid (HA). In this study, the effect of Ca(2+) on the colloidal stability of NZVI coated with three types of stabilizers (i.e., polyacrylic acid (PAA), Tween-20 and starch) was evaluated in the absence or presence of HA. Differing stability behavior was observed for different surface-modified NZVIs. The presence of Ca(2+) exerted a slight influence on the settling of NZVI modified with PAA or Tween-20, in the absence or presence of HA. However, the presence of Ca(2+) caused significant aggregation and sedimentation for starch-modified NZVI in the absence of HA, and induced an even higher degree of aggregation and sedimentation in the presence of HA. It is presumed that, in the absence of HA, starch-modified NZVI particles undergo attachment with each other via Ca(2+) complexation with the coated starch molecules on the surface of the particles, thus enhancing the aggregation and the following sedimentation of starch-modified NZVI. However, in the presence of HA, spectroscopic analysis of the starch-modified NZVI aggregates indicated that the bridging interaction of HA with Ca(2+) was the predominant mechanism for the enhanced aggregation. PMID:23466217

  20. Removal of organic compounds and trace metals from oil sands process-affected water using zero valent iron enhanced by petroleum coke.

    PubMed

    Pourrezaei, Parastoo; Alpatova, Alla; Khosravi, Kambiz; Drzewicz, Przemysław; Chen, Yuan; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

    2014-06-15

    The oil production generates large volumes of oil sands process-affected water (OSPW), referring to the water that has been in contact with oil sands or released from tailings deposits. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. Zero valent iron alone (ZVI) and in combination with petroleum coke (CZVI) were investigated as environmentally friendly treatment processes for the removal of naphthenic acids (NAs), acid-extractable fraction (AEF), fluorophore organic compounds, and trace metals from OSPW. While the application of 25 g/L ZVI to OSPW resulted in 58.4% removal of NAs in the presence of oxygen, the addition of 25 g petroleum coke (PC) as an electron conductor enhanced the NAs removal up to 90.9%. The increase in ZVI concentration enhanced the removals of NAs, AEF, and fluorophore compounds from OSPW. It was suggested that the electrons generated from the oxidation of ZVI were transferred to oxygen, resulting in the production of hydroxyl radicals and oxidation of NAs. When OSPW was de-oxygenated, the NAs removal decreased to 17.5% and 65.4% during treatment with ZVI and CZVI, respectively. The removal of metals in ZVI samples was similar to that obtained during CZVI treatment. Although an increase in ZVI concentration did not enhance the removal of metals, their concentrations effectively decreased at all ZVI loadings. The Microtox(®) bioassay with Vibrio fischeri showed a decrease in the toxicity of ZVI- and CZVI-treated OSPW. The results obtained in this study showed that the application of ZVI in combination with PC is a promising technology for OSPW treatment. PMID:24681364

  1. In situ remediation-released zero-valent iron nanoparticles impair soil ecosystems health: A C. elegans biomarker-based risk assessment.

    PubMed

    Yang, Ying-Fei; Cheng, Yi-Hsien; Liao, Chung-Min

    2016-11-01

    There is considerable concern over the potential ecotoxicity to soil ecosystems posed by zero-valent iron nanoparticles (Fe(0) NPs) released from in situ environmental remediation. However, a lack of quantitative risk assessment has hampered the development of appropriate testing methods used in environmental applications. Here we present a novel, empirical approach to assess Fe(0) NPs-associated soil ecosystems health risk using the nematode Caenorhabditis elegans as a model organism. A Hill-based dose-response model describing the concentration-fertility inhibition relationships was constructed. A Weibull model was used to estimate thresholds as a guideline to protect C. elegans from infertility when exposed to waterborne or foodborne Fe(0) NPs. Finally, the risk metrics, exceedance risk (ER) and risk quotient (RQ) of Fe(0) NPs in various depths and distances from remediation sites can then be predicted. We showed that under 50% risk probability (ER=0.5), upper soil layer had the highest infertility risk (95% confidence interval: 13.18-57.40%). The margins of safety and acceptable criteria for soil ecosystems health for using Fe(0) NPs in field scale applications were also recommended. Results showed that RQs are larger than 1 in all soil layers when setting a stricter threshold of ∼1.02mgL(-1) of Fe(0) NPs. This C. elegans biomarker-based risk model affords new insights into the links between widespread use of Fe(0) NPs and environmental risk assessment and offers potential environmental implications of metal-based NPs for in situ remediation. PMID:27281168

  2. Three-dimensional honeycomb-like structured zero-valent iron/chitosan composite foams for effective removal of inorganic arsenic in water.

    PubMed

    Su, Fengchao; Zhou, Hongjian; Zhang, Yunxia; Wang, Guozhong

    2016-09-15

    A facile freeze-drying method was presented to fabricate three dimensional (3D) honeycomb-like structured nanoscale zero-valent iron/chitosan composite foams (ICCFs) for effective removal of inorganic arsenic in water. It was found that freezing temperature has important influence on the formation of 3D network structure of ICCFs. The ICCFs obtained at freeze temperature of -80°C exhibits oriented porous structure with good mechanical property than that at -20°C, thus improved excellent removal capability of As(III) and As(V) up to 114.9mgg(-1) and 86.87mgg(-1), respectively. Further, the adsorption kinetics of ICCFs on As(III) and As(V) can be described by pseudo-second order model and their adsorption isotherms follow Langmuir adsorption model. The superior removal performance of ICCFs on As(III) and As(V) can be ascribed to its oriented porous structure with abundant adsorption active sites resulted from nZVI and O, N-containing functional groups in ICCFs. Importantly, it was found that the O, N-containing functional groups of chitosan in ICCFs can adequately bind with the dissolved Fe(3+) ions from oxidation of nZVI to form Fe(3+)-Chitosan complex during removal of As(III) and As(V), thus effectively avoiding the dissolved Fe(3+) ions into solution to produce secondary pollution. A possible adsorption-coupled reduction mechanism of ICCFs on As(III) and As(V) was also proposed based on the experimental results. We believe that this work would be helpful to develop low-cost and abundant chitosan-based materials as high performance adsorbents for environmental remediation applications. PMID:27362398

  3. Effects of nano-sized zero-valent iron (nZVI) on DDT degradation in soil and its toxicity to collembola and ostracods.

    PubMed

    El-Temsah, Yehia S; Joner, Erik J

    2013-06-01

    Nano-sized zero valent iron (nZVI) has been studied for in situ remediation of contaminated soil and ground water. However, little is known about its effects on organisms in soil and aquatic ecosystems. In this study, the effect of nZVI on degradation of DDT and its ecotoxicological effects on collembola (Folsomia candida) and ostracods (Heterocypris incongruens) were investigated. Two soils were used in suspension incubation experiments lasting for 7 and 30 d; a spiked (20 mg DDT kg(-1)) sandy soil and an aged (>50 years) DDT-polluted soil (24 mg DDT kg(-1)). These were incubated with 1 or 10 g nZVI kg(-1), and residual toxicity in soil and the aqueous phase tested using ecotoxicological tests with collembola or ostracods. Generally, addition of either concentration of nZVI to soil led to about 50% degradation of DDT in spiked soil at the end of 7 and 30 d incubation, while the degradation of DDT was less in aged DDT-polluted soil (24%). Severe negative effects of nZVI were observed on both test organisms after 7 d incubation, but prolonged incubation led to oxidation of nZVI which reduced its toxic effects on the tested organisms. On the other hand, DDT had significant negative effects on collembolan reproduction and ostracod development. We conclude that 1 g nZVI kg(-1) was efficient for significant DDT degradation in spiked soil, while a higher concentration was necessary for treating aged pollutants in soil. The adverse effects of nZVI on tested organisms seem temporary and reduced after oxidation. PMID:23522781

  4. 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...

  5. Degradation of bromothymol blue by 'greener' nano-scale zero-valent iron synthesized using tea polyphenols

    EPA Science Inventory

    A green single-step synthesis of iron nanoparticles using tea (Camellia sinensis) polyphenols is described that uses no added surfactants/polymers as a capping or reducing agents. The expeditious reaction between polyphenols and ferric nitrate occurs within few minutes at room te...

  6. Incorporation of zero valent iron nanoparticles in the matrix of cationic resin beads for the remediation of Cr(VI) contaminated waters.

    PubMed

    Toli, Aikaterini; Chalastara, Konstantina; Mystrioti, Christiana; Xenidis, Anthimos; Papassiopi, Nymphodora

    2016-07-01

    The objective of present study was to obtain the fixation of nano zero valent iron (nZVI) particles on a permeable matrix and evaluate the performance of this composite material for the removal of Cr(VI) from contaminated waters. The experiments were carried out using the cationic resin Dowex 50WX2 as porous support of the iron nanoparticles. The work was carried out in two phases. The first phase involved the fixation of nZVI on the resin matrix. The resin granules were initially mixed with a FeCl3 solution to obtain the adsorption of Fe(III). Then the Fe(III) loaded resin (RFe) was treated with polyphenol solutions to obtain the reduction of Fe(III) to the elemental state. Two polyphenol solutions were tested as reductants, i.e. green tea extract and gallic acid. Green tea was found to be inefficient, probably due to the relatively big size of the contained polyphenol molecules, but gallic acid molecules were able to reach adsorbed Fe(III) and reduce the cations to the elemental state. The second phase was focused on the investigation of Cr(VI) reduction kinetics using the nanoiron loaded resins (R-nFe). It was found that the reduction follows a kinetic law of first order with respect to Cr(VI) and to the embedded nanoiron. Compared to other similar products, this composite material was found to have comparable performance regarding reaction rates and higher degree of iron utilization. Namely the rate constant for the reduction of Cr(VI), in the presence of 1 mM nZVI, was equivalent to 1.4 h of half-life time at pH 3.2 and increased to 24 h at pH 8.5. The degree of iron utilization was as high as 0.8 mol of reduced Cr(VI) per mole of iron. It was also found that this composite material can be easily regenerated and reused for Cr(VI) reduction without significant loss of efficiency. PMID:27108046

  7. ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: KINETICS, REDOX TRANSFORMATION, AND IMPLICATIONS FOR IN SITU GROUNDWATER REMEDIATION

    EPA Science Inventory

    Batch tests were performed utilizing four zerovalent iron (Fe0) filings (Fisher, Peerless, Master Builders, and Aldrich) to remove As(V) and As(III) from water. One gram of metal was reacted headspace-free at 23 °C for up to 5 days in the dark with 41.5 mL of 2 mg L-1 As(V), or A...

  8. Removal of co-present chromate and arsenate by zero-valent iron in groundwater with humic acid and bicarbonate.

    PubMed

    Liu, Tongzhou; Rao, Pinhua; Mak, Mark S H; Wang, Peng; Lo, Irene M C

    2009-05-01

    The interactions of co-present Cr(VI) and As(V), and the influences of humic acid and bicarbonate in the process of Cr(VI) and As(V) removal by Fe(0) were investigated in a batch setting using simulated groundwater with 5 mM NaCl, 1 mM Na(2)SO(4), and 0.8 mM CaCl(2) as background electrolytes at an initial pH value of 7. Cr(VI) and As(V) were observed to be subject to different impacts induced by co-existing As(V) or Cr(VI), humic acid and bicarbonate, originating from their distinct removal mechanisms by Fe(0). Cr(VI) removal is a reduction-dominated process, whereas As(V) removal principally involves adsorption onto iron corrosion products. Experimental results showed that Cr(VI) removal was not affected by the presence of As(V) and humic acid. However, As(V) removal appeared to be inhibited by co-present Cr(VI). When the Cr(VI) concentration was 2, 5, and 10 mg/L, in the absence of humic acid and bicarbonate, As(V) removal rate constants were decreased by 27.9%, 49.0%, and 61.2%, respectively, which probably resulted from competition between Cr(VI) and As(V) for adsorption sites of the iron corrosion products. Furthermore, the presence of humic acid significantly varied As(V) removal kinetics by delaying the formation and aggregation of iron hydroxides due to the formation of soluble Fe-humate complexes and stably dispersed fine iron hydroxides colloids. In the presence of bicarbonate, both Cr(VI) and As(V) removal was increased and the inhibitory effect of Cr(VI) on As(V) removal was suppressed, resulting from the buffering effects and the promoted iron corrosion induced by bicarbonate, and the formation of CaCO(3) in solution, which enhanced As(V) adsorption. PMID:19321187

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

    PubMed Central

    2014-01-01

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

  10. Removal of uranium (VI) from aqueous systems by nanoscale zero-valent iron particles suspended in carboxy-methyl cellulose

    NASA Astrophysics Data System (ADS)

    Popescu (Hoştuc), Ioana-Carmen; Filip, Petru; Humelnicu, Doina; Humelnicu, Ionel; Scott, Thomas Bligh; Crane, Richard Andrew

    2013-11-01

    Carboxy-methyl-cellulose (CMC), a common "delivery vehicle" for the subsurface deployment of iron nanoparticles (INP) has been tested in the current work for the removal of aqueous uranium from synthetic water samples. A comparison of the removal of aqueous uranium from solutions using carboxy-methyl-cellulose with and without iron nanoparticles (CMC-INP and CMC, respectively) was tested over a 48 h reaction period. Analysis of liquid samples using spectrophotometry determined a maximum sorption capacity of uranium, Qmax, of 185.18 mg/g and 322.58 mg/g for CMC and CMC-INP respectively, providing strong evidence of an independent aqueous uranium removal ability exhibited by CMC. The results point out that CMC provides an additional capacity for aqueous uranium removal. Further tests are required to determine whether similar behaviour will be observed for other aqueous contaminant species and if the presence of CMC within a INP slurry inhibits or aids the reactivity, reductive capacity and affinity of INP for aqueous contaminant removal.

  11. Zero-valent iron doped carbons readily developed from sewage sludge for lead removal from aqueous solution.

    PubMed

    Su, Yiming; Sun, Xiaoya; Zhou, Xuefei; Dai, Chaomeng; Zhang, Yalei

    2015-10-01

    Low-cost but high-efficiency composites of iron-containing porous carbons were prepared using sewage sludge and ferric salts as raw materials. Unlike previous time- and energy-consuming manufacturing procedures, this study shows that pyrolyzing a mixture of sludge and ferric salt can produce suitable composites for lead adsorption. The specific surface area, the total pore volume and the average pore width of the optimal composite were 321m(2)/g, 0.25cm(3)/g, and 3.17nm, respectively. X-ray diffraction analysis indicated that ferric salt favored the formation of metallic iron, while Fourier transform infrared spectroscopy revealed the formation of hydroxyl and carboxylic groups. The result of batch tests indicated that the adsorption capacity of carbons activated with ferric salt could be as high as 128.9mg/g, while that of carbons without activation was 79.1mg/g. The new manufacturing procedure used in this study could save at least 19.5kJ of energy per gram of activated carbon. PMID:26456600

  12. Field Application of Nanoscale Zero-Valent Iron Particles to In-Situ Treatment of Trichloroethylene in an Aquifer with an Oxic Condition

    NASA Astrophysics Data System (ADS)

    Ahn, J.; Kim, C.; Huynh, T. N.; Hwang, I.

    2013-12-01

    Nanoscale zero-valent iron (NZVI) is a promising reactive medium for rapid in situ remediation of various contaminants including chlorinated solvents, in the groundwater and soil. However, once NZVI particles are injected into an aquifer, they can have poor mobility and reactivity due to their aggregation tendency and to interactions with groundwater solutes such as anions, dissolved organic matter (NOM), and oxygen. Therefore, key technical challenges in the field application are to distribute NZVI particles effectively within the contaminated area, and to maintain the reactivity of NZVI particles while they are delivered. Field studies were conducted to evaluate: (i) mobility of a polymer-coated NZVI in an aquifer with a strong oxic condition, (ii) effect of dissolved oxygen on the degradation of TCE, and (iii) effects of dissolved anions and oxygen on the sustainability of injected NZVI. Initially, natural gradient and forced gradient tracer tests were carried out to investigate the hydrogeological characteristics of the site before injecting NZVI. Preferential flow paths of the groundwater identified by the tracer tests were towards northeast and northwest. The NZVI slurry was then prepared on site and injected at a concentration of up to 10 g/L into the subsurface having area of 140 ft2. A total of approximately 66 pounds of the coated NZVI were successfully injected. During the field injections, NZVI particles were observed in a monitoring well located 13 feet downgradient from the injection well. Iron monitoring data showed that the NZVI could reasonably be delivered under the oxic condition that could enhance the formation of iron oxides, which could be deleterious for the NZVI transport. TCE degradation was more active at the wells with high DO concentrations, based on the correlation between TCE concentrations and DO or NZVI concentrations. It was suspected that solid or liquid form of ferrous ion from the oxidation of NZVI caused a Fenton reaction in

  13. Simple combination of oxidants with zero-valent-iron (ZVI) achieved very rapid and highly efficient removal of heavy metals from water.

    PubMed

    Guo, Xuejun; Yang, Zhe; Dong, Haiyang; Guan, Xiaohong; Ren, Qidong; Lv, Xiaofang; Jin, Xin

    2016-01-01

    This study, for the first time, demonstrated a continuously accelerated Fe(0) corrosion driven by common oxidants (i.e., NaClO, KMnO4 or H2O2) and thereby the rapid and efficient removal of heavy metals (HMs) by zero-valent iron (ZVI) under the experimental conditions of jar tests and column running. ZVI simply coupled with NaClO, KMnO4 or H2O2 (0.5 mM) resulted in almost complete As(V) removal within only 10 min with 1000 μg/L of initial As(V) at initial pH of 7.5(±0.1) and liquid solid ratio of 200:1. Simultaneous removal of 200 μg/L of initial Cd(II) and Hg(II) to 2.4-4.4 μg/L for Cd(II) and to 4.0-5.0 μg/L for Hg(II) were achieved within 30 min. No deterioration of HM removal was observed during the ten recycles of jar tests. The ZVI columns activated by 0.1 mM of oxidants had stably treated 40,200 (NaClO), 20,295 (KMnO4) and 40,200 (H2O2) bed volumes (BV) of HM-contaminated drinking water, but with no any indication of As breakthrough (<10 μg/L) even at short empty bed contact time (EBCT) of 8.0 min. The high efficiency of HMs removal from both the jar tests and column running implied a continuous and stable activation (overcoming of iron passivation) of Fe(0) surface by the oxidants. Via the proper increase in oxidant dosing, the ZVI/oxidant combination was applicable to treat highly As(V)-contaminated wastewater. During Fe(0) surface corrosion accelerated by oxidants, a large amount of fresh and reactive iron oxides and oxyhydroxides were continuously generated, which were responsible for the rapid and efficient removal of HMs through multiple mechanisms including adsorption and co-precipitation. A steady state of Fe(0) surface activation and HM removal enabled this simply coupled system to remove HMs with high speed, efficiency and perdurability. PMID:26575476

  14. Monitoring the injection of microscale zero-valent iron particles for groundwater remediation by means of complex electrical conductivity imaging

    NASA Astrophysics Data System (ADS)

    Flores Orozco, A.; Velimirovic, M.; Tosco, T.; Kemna, A.; Sapion, H.; Klaas, N.; Sethi, R.; Bastiaens, L.

    2015-12-01

    The injection of nano- and microscale zerovalent iron (ZVI) particles has emerged as a promising technique for groundwater remediation. In particular, ZVI injections offer a suitable alternative for the remediation of areas not accessible with other techniques, such as areas characterized by low hydraulic conductivity. In such cases, the injection is performed at high pressure in order to create preferential flow paths (i.e., fractures). Particle injection via fracturing demands an adequate monitoring of the ZVI delivery to track the migration path of the particles as well as to delineate the extension and distribution of the iron slurry. However, characterization of ZVI injections is to date based mainly on the analysis of groundwater and soil samples, thus, limiting the spatio-temporal resolution of the investigation and making it not suitable for real-time monitoring. To overcome this, here we present the application of the complex conductivity (CC) imaging method to characterize the delivery of guar gum stabilized microscale ZVI (GG-mZVI) particles during a field-scale injection by hydraulic fracturing. Our results demonstrated that CC images provide not only an improved characterization of the contaminant distribution, but also valuable information to identify the migration pathway of the injected GG-mZVI. The relatively short acquisition time of CC datasets permitted to obtain monitoring data with enhanced temporal resolution, i.e., after each injection (every ~15 minutes), while still covering an extended area of investigation in comparison to conventional geochemical monitoring by means of soil and water samples. As presented in Figure 1, the CC images revealed an increase (~20%) in the induced electrical polarization (Φ), upon delivery of ZVI into the targeted area, due to the accumulation of ZVI. Furthermore, larger changes (>50%) occurred in shallow sediments, a few meters away from the injection, suggesting the migration of particles through

  15. Synthesis of granular activated carbon/zero valent iron composites for simultaneous adsorption/dechlorination of trichloroethylene.

    PubMed

    Tseng, Hui-Hsin; Su, Jhih-Gang; Liang, Chenju

    2011-08-30

    The coupling adsorption and degradation of trichloroethylene (TCE) through dechlorination using synthetic granular activated carbon and zerovalent iron (GAC-ZVI) composites was studied. The GAC-ZVI composites were prepared from aqueous Fe(2+) solutions by impregnation with and without the use of a PEG dispersant and then heated at 105°C or 700°C under a stream of N(2). Pseudo-first-order rate constant data on the removal of TCE demonstrates that the adsorption kinetics of GAC is similar to those of GAC-ZVI composites. However, the usage of GAC-ZVI composites liberated a greater amount of Cl than when ZVI was used alone. The highest degree of reductive dechlorination of TCE was achieved using a GAC-ZVI700P composite (synthesized using PEG under 700°C). A modified Langmuir-Hinshelwood rate law was employed to depict the behavior of Cl liberation. As a result, a zero-order Cl liberation reaction was observed and the desorption limited TCE degradation rate constant decreased as the composite dosage was increased. The GAC-ZVI composites can be employed as a reactive GAC that is not subject to the limitations of using GAC and ZVI separately. PMID:21676545

  16. Degradation of chlorinated organic solvents in aqueous percarbonate system using zeolite supported nano zero valent iron (Z-nZVI) composite.

    PubMed

    Danish, Muhammad; Gu, Xiaogang; Lu, Shuguang; Naqvi, Muhammad

    2016-07-01

    Chlorinated organic solvents (COSs) are extensively detected in contaminated soil and groundwater that pose long-term threats to human life and environment. In order to degrade COSs effectively, a novel catalytic composite of natural zeolite-supported nano zero valent iron (Z-nZVI) was synthesized in this study. The performance of Z-nZVI-catalyzed sodium percarbonate (SPC) in a heterogeneous Fenton-like system was investigated for the degradation of COSs such as 1,1,1-trichloroethane (1,1,1-TCA) and trichloroethylene (TCE). The surface characteristics and morphology of the Z-nZVI composite were tested using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Total pore volume, specific surface area, and pore size of the natural zeolite and the Z-nZVI composite were measured using Brunauer-Emmett-Teller (BET) method. SEM and TEM analysis showed significant elimination of aggregation and well dispersion of iron nano particles on the framework of natural zeolite. The BET N2 measurement analysis indicated that the surface area of the Z-nZVI composite was 72.3 m(2)/g, much larger than that of the natural zeolite (0.61 m(2)/g). For the contaminant analysis, the samples were extracted with n-hexane and analyzed through gas chromatograph. The degradation of 1,1,1-TCA and TCE in the Z-nZVI-catalyzed percarbonate system were 48 and 39 % respectively, while strong augmentation was observed up to 83 and 99 %, respectively, by adding the reducing agent (RA), hydroxyl amine (NH2OH•HCl). Probe tests validated the presence of OH(●) and O2 (●-) which were responsible for 1,1,1-TCA and TCE degradation, whereas both free radicals were strengthened with the addition of RA. In conclusion, the Z-nZVI/SPC oxidation with reducing agent shows potential technique for degradation of groundwater contaminated by 1,1,1-TCA and TCE. PMID:27023817

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

    PubMed

    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 2m length were performed with initial Darcy injection velocities (q0) of 0.5, 1.5, and 4.1m/h and elemental iron input concentrations (Fe(0)in) of 0.6, 10, and 17g/L. Concentrations of Fe(0) in the sand were determined by magnetic susceptibility scans, which provide detailed Fe(0) 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 Fe(0) concentrations of about 14-18g/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

  18. 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

  19. 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

  20. Biogenic nano-magnetite and nano-zero valent iron treatment of alkaline Cr(VI) leachate and chromite ore processing residue

    PubMed Central

    Watts, Mathew P.; Coker, Victoria S.; Parry, Stephen A.; Pattrick, Richard A.D.; Thomas, Russell A.P.; Kalin, Robert; Lloyd, Jonathan R.

    2015-01-01

    Highly reactive nano-scale biogenic magnetite (BnM), synthesized by the Fe(III)-reducing bacterium Geobacter sulfurreducens, was tested for the potential to remediate alkaline Cr(VI) contaminated waters associated with chromite ore processing residue (COPR). The performance of this biomaterial, targeting aqueous Cr(VI) removal, was compared to a synthetic alternative, nano-scale zero valent iron (nZVI). Samples of highly contaminated alkaline groundwater and COPR solid waste were obtained from a contaminated site in Glasgow, UK. During batch reactivity tests, Cr(VI) removal from groundwater was inhibited by ∼25% (BnM) and ∼50% (nZVI) when compared to the treatment of less chemically complex model pH 12 Cr(VI) solutions. In both the model Cr(VI) solutions and contaminated groundwater experiments the surface of the nanoparticles became passivated, preventing complete coupling of their available electrons to Cr(VI) reduction. To investigate this process, the surfaces of the reacted samples were analyzed by TEM-EDX, XAS and XPS, confirming Cr(VI) reduction to the less soluble Cr(III) on the nanoparticle surface. In groundwater reacted samples the presence of Ca, Si and S was also noted on the surface of the nanoparticles, and is likely responsible for earlier onset of passivation. Treatment of the solid COPR material in contact with water, by addition of increasing weight % of the nanoparticles, resulted in a decrease in aqueous Cr(VI) concentrations to below detection limits, via the addition of ⩾5% w/w BnM or ⩾1% w/w nZVI. XANES analysis of the Cr K edge, showed that the % Cr(VI) in the COPR dropped from 26% to a minimum of 4–7% by the addition of 5% w/w BnM or 2% w/w nZVI, with higher additions unable to reduce the remaining Cr(VI). The treated materials exhibited minimal re-mobilization of soluble Cr(VI) by re-equilibration with atmospheric oxygen, with the bulk of the Cr remaining in the solid fraction. Both nanoparticles exhibited a considerable

  1. Aquifer modification: an approach to improve the mobility of nanoscale zero-valent iron particles used for in situ groundwater remediation

    NASA Astrophysics Data System (ADS)

    MicicBatka, Vesna; Schmid, Doris; Marko, Florian; Velimirovic, Milica; Wagner, Stephan; von der Kammer, Frank; Hofmann, Thilo

    2015-04-01

    Successful emplacement of nanoscale zero-valent iron (nZVI) within the contaminated source zone is a prerequisite for the use of nZVI technology in groundwater remediation. Emplacement of nZVI is influenced i.e., by the injection technique and the injection velocity applied, as well as by the mobility of nZVI in the subsurface. Whereas processes linked to the injection can be controlled by the remediation practitioners, the mobility of nZVI in the subsurface remains limited. Even though mobility of nZVI is somewhat improved by surface coating with polyelectrolytes, it is still greatly affected by the groundwater composition and physical and chemical heterogeneities of aquifer grains. In order to promote mobility of nZVI it is needed to alter the surface charge heterogeneities of aquifer grains. Modifying the aquifer grain's surfaces by means of polyelectrolyte coating is an approach proposed to increase the overall negative surface charge of the aquifer grain surfaces, hinder deposition of nZVI onto aquifer grains, and finally promote nZVI mobility. In this study the effect of different polyelectrolytes on the nZVI mobility is tested in natural sands deriving from real brownfield sites that are proposed to be remediated using the nZVI technology. Sands collected from brownfield sites were characterized in terms of grain size distribution, mineralogical and chemical composition, and organic carbon content. Furthermore, surface charge of these sands was determined in both, low- and high ionic strength background solutions. Finally, changes of the sand's surface charges were examined after addition of the proposed aquifer modifiers, lignin sulfonate and humic acid. Surface charge of brownfield sands in low ionic strength background solution is more negative compared to that in high ionic strength background solution. An increase in negative surface potential of brownfield sand was recorded when aquifer modifiers were applied in a background solution with low ionic

  2. 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. PMID:26521089

  3. An insight in magnetic field enhanced zero-valent iron/H2O2 Fenton-like systems: Critical role and evolution of the pristine iron oxides layer

    PubMed Central

    Xiang, Wei; Zhang, Beiping; Zhou, Tao; Wu, Xiaohui; Mao, Juan

    2016-01-01

    This study demonstrated the synergistic degradation of 4-chlorophenol (4-CP) achieved in a magnetic field (MF) enhanced zero-valent iron (ZVI)/H2O2 Fenton-like (FL) system and revealed an interesting correlative dependence relationship between MF and the pristine iron oxides layer (FexOy) on ZVI particles. First, a comparative investigation between the FL and MF-FL systems was conducted under different experimental conditions. The MF-FL system could suppress the duration of initial lag degradation phase one order of magnitude in addition of the significant enhancement in overall 4-CP degradation. Monitoring of intermediates/products indicated that MF would just accelerate the Fenton reactions to produce hydroxyl radical more rapidly. Evolutions of simultaneously released dissolved iron species suggested that MF would not only improve mass-transfer of the initial heterogeneous reactions, but also modify the pristine ZVI surface. Characterizations of the specific prepared ZVI samples evidenced that MF would induce a special evolution mechanism of the ZVI particles surface depending on the existence of FexOy layer. It comprised of an initial rapid point dissolution of FexOy and a following pitting corrosion of the exposed Fe0 reactive sites, finally leading to appearance of a particular rugged surface topography with numerous adjacent Fe0 pits and FexOy tubercles. PMID:27053228

  4. An insight in magnetic field enhanced zero-valent iron/H2O2 Fenton-like systems: Critical role and evolution of the pristine iron oxides layer.

    PubMed

    Xiang, Wei; Zhang, Beiping; Zhou, Tao; Wu, Xiaohui; Mao, Juan

    2016-01-01

    This study demonstrated the synergistic degradation of 4-chlorophenol (4-CP) achieved in a magnetic field (MF) enhanced zero-valent iron (ZVI)/H2O2 Fenton-like (FL) system and revealed an interesting correlative dependence relationship between MF and the pristine iron oxides layer (FexOy) on ZVI particles. First, a comparative investigation between the FL and MF-FL systems was conducted under different experimental conditions. The MF-FL system could suppress the duration of initial lag degradation phase one order of magnitude in addition of the significant enhancement in overall 4-CP degradation. Monitoring of intermediates/products indicated that MF would just accelerate the Fenton reactions to produce hydroxyl radical more rapidly. Evolutions of simultaneously released dissolved iron species suggested that MF would not only improve mass-transfer of the initial heterogeneous reactions, but also modify the pristine ZVI surface. Characterizations of the specific prepared ZVI samples evidenced that MF would induce a special evolution mechanism of the ZVI particles surface depending on the existence of FexOy layer. It comprised of an initial rapid point dissolution of FexOy and a following pitting corrosion of the exposed Fe(0) reactive sites, finally leading to appearance of a particular rugged surface topography with numerous adjacent Fe(0) pits and FexOy tubercles. PMID:27053228

  5. An insight in magnetic field enhanced zero-valent iron/H2O2 Fenton-like systems: Critical role and evolution of the pristine iron oxides layer

    NASA Astrophysics Data System (ADS)

    Xiang, Wei; Zhang, Beiping; Zhou, Tao; Wu, Xiaohui; Mao, Juan

    2016-04-01

    This study demonstrated the synergistic degradation of 4-chlorophenol (4-CP) achieved in a magnetic field (MF) enhanced zero-valent iron (ZVI)/H2O2 Fenton-like (FL) system and revealed an interesting correlative dependence relationship between MF and the pristine iron oxides layer (FexOy) on ZVI particles. First, a comparative investigation between the FL and MF-FL systems was conducted under different experimental conditions. The MF-FL system could suppress the duration of initial lag degradation phase one order of magnitude in addition of the significant enhancement in overall 4-CP degradation. Monitoring of intermediates/products indicated that MF would just accelerate the Fenton reactions to produce hydroxyl radical more rapidly. Evolutions of simultaneously released dissolved iron species suggested that MF would not only improve mass-transfer of the initial heterogeneous reactions, but also modify the pristine ZVI surface. Characterizations of the specific prepared ZVI samples evidenced that MF would induce a special evolution mechanism of the ZVI particles surface depending on the existence of FexOy layer. It comprised of an initial rapid point dissolution of FexOy and a following pitting corrosion of the exposed Fe0 reactive sites, finally leading to appearance of a particular rugged surface topography with numerous adjacent Fe0 pits and FexOy tubercles.

  6. Comparison of U(VI) adsorption onto nanoscale zero-valent iron and red soil in the presence of U(VI)-CO3/Ca-U(VI)-CO3 complexes.

    PubMed

    Zhang, Zhibin; Liu, Jun; Cao, Xiaohong; Luo, Xuanping; Hua, Rong; Liu, Yan; Yu, Xiaofeng; He, Likai; Liu, Yunhai

    2015-12-30

    The influence of U(VI)-CO3 and Ca-U(VI)-CO3 complexes on U(VI) adsorption onto red soil and nanoscale zero-valent iron (NZVI) was investigated using batch adsorption and fixed-bed column experiments to simulate the feasibility of NZVI as the reactive medium in permeable- reactive barriers (PRB) for in situ remediation of uranium-contaminated red soils. The adsorption capacity (qe) and distribution constant (Kd) of NZVI and red soil decreased with increasing pH, dissolved carbonate and calcium concentrations, but the qe and Kd values of NZVI were 5-10 times higher than those of red soil. The breakthrough pore volume (PV) values increased with the decrease of pH, dissolved carbonate and calcium concentration; however, the breakthrough PV values of the PRB column filled with 5% NZVI were 2.0-3.5 times higher than the 100% red soil column. The U(VI)-CO3 complexes adsorbed onto the surface of red soil/NZVI (≡SOH) to form SO-UO2CO3(-) or SO-UO2 (CO3)2(3-). XPS and XRD analysis further confirmed the reduction of U(VI) to U(IV) and the formation of FeOOH on NZVI surfaces. The findings of this study are significant to the remediation of uranium-contaminated red soils and the consideration of practical U(VI) species in the natural environment. PMID:26280584

  7. Enhanced zero-valent metal permeable wall treatment of contaminated groundwater

    SciTech Connect

    Reinhart, D.R.; Clausen, C.A.; Geiger, C.

    1997-12-31

    On-going research at the University of Central Florida, supported by NASA, is investigating the use of sonicated zero-valent metal permeable treatment walls to remediate chlorinated solvent contaminated groundwater. Use of ultrasound within the treatment wall is proposed to enhance and/or restore the activity of the zero-valent metal. Batch studies designed to evaluate the destruction of chlorinated hydrocarbons using enhanced zero-valent metal reduction found a nearly three-fold increase in reaction rates after ultrasound treatment. Column studies substantiated these results. It is hypothesized that ultrasound serves to remove corrosion products from the iron surface and will prolong the reactive life and efficiency of the permeable treatment wall, thus decreasing long-term costs of wall construction and maintenance.

  8. ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: EFFECTS OF PHOSPHATE, SILICATE, CARBONATE, BORATE, SULFATE, CHROMATE, MOLYBDATE, AND NITRATE, RELATIVE TO CHLORIDE

    EPA Science Inventory

    Batch tests were performed to evaluate the effects of inorganic anion competition on the kinetics of arsenate (As(V)) and arsenite (As(III)) removal by zerovalent iron (Peerless Fe0) in aqueous solution. The oxyanions underwent either sorption-dominated reactions (phosphate, sil...

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

    SciTech Connect

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

    2014-12-01

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

  10. Reduction and immobilization of radionuclides and toxic metal ions using combined zero valent iron and anaerobic bacteria. Year one technical progress report

    SciTech Connect

    Weathers, L.J.; Katz, L.E.

    1997-10-01

    'The objective of this project is to design a combined abiotic/microbial, reactive, permeable, in-situ barrier with sufficient reductive potential to prevent downgradient migration of toxic metal ions. The field-scale application of this technology would utilize anaerobic digester sludge, Fe(O) particles for supporting anaerobic biofilms, and suitable aquifer material for construction of the barrier. The major goals for Year 1 were to establish the sulfate reducing mixed culture, to obtain sources of iron metal, and to conduct background experiments which will establish baseline rates for abiotic chromium reduction rates. Research completed to date is described.'

  11. Reductive dechlorination of octachlorodibenzo-p-dioxin by nanosized zero-valent zinc: modeling of rate kinetics and congener profile.

    PubMed

    Bokare, Varima; Jung, Ju-Lim; Chang, Yoon-Young; Chang, Yoon-Seok

    2013-04-15

    Polychlorinated dibenzo-p-dioxins (PCDDs), a group of recalcitrant toxic compounds, are ubiquitous in nature. Amongst them, octachlorodibenzo-p-dioxin (OCDD) is not only prevalent in soil and sediment due to its high lipophilicity and hydrophobicity, but also detected in ground water and surface water. The present study examined the degradation of OCDD in aqueous solutions using four different zero-valent metal nanoparticles; zero-valent aluminum (nZVAL), zero-valent zinc (nZVZ), zero-valent iron (nZVI) and zero-valent nickel (nZVN). Only nZVZ was found to efficiently degrade OCDD into lower chlorinated congeners [OCDD → 1,2,3,4,6,7,9-HxCDD (63%)→ 1,2,3,6,8,9-HpCDD (21%) → 1,2,4,7,8-PeCDD (46%) → 1,2,4,7-TeCDD (19%)] under ambient conditions. Simulations were also performed to predict the OCDD dechlorination pathway using a linear free energy relationship (LFER) model. Additionally, toxic equivalent quantity (TEQ) and homologue patterns were calculated by LFER modeling. The experimentally observed congener profiles were in excellent agreement with the model-predicted results, especially considering the complexity of the OCDD dechlorination pathway (256 theoretically possible reactions). This study proposes nZVZ as a suitable candidate for OCDD dechlorination and constitutes the first report on OCDD degradation using zero-valent metal nanoparticles under ambient conditions. PMID:23500419

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

    PubMed

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

    2016-07-19

    Nanoscale zerovalent iron (nZVI) is an emerging technology for the remediation of contaminated sites. However, there are concerns related to the impact of nZVI on in situ microbial communities. In this study, the microbial community composition at a contaminated site was monitored over two years following the injection of nZVI stabilized with carboxymethyl cellulose (nZVI-CMC). Enhanced dechlorination of chlorinated ethenes to nontoxic ethene was observed long after the expected nZVI oxidation. The abundance of Dehalococcoides (Dhc) and vinyl chloride reductase (vcrA) genes, monitored using qPCR, increased by over an order of magnitude in nZVI-CMC-impacted wells. The entire microbial community was tracked using 16S rRNA gene amplicon pyrosequencing. Following nZVI-CMC injection, a clear shift in microbial community was observed, with most notable increases in the dechlorinating genera Dehalococcoides and Dehalogenimonas. This study suggests that coupled abiotic degradation (i.e., from reaction with nZVI) and biotic degradation fueled by CMC led to the long-term degradation of chlorinated ethenes at this field site. Furthermore, nZVI-CMC addition stimulated dehalogenator growth (e.g., Dehalococcoides) and biotic degradation of chlorinated ethenes. PMID:27305345

  13. Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Khan, Ayub; Wang, Pengyi; Liu, Yunhai; Alsaedi, Ahmed; Hayat, Tasawar; Wang, Xiangke

    2016-07-19

    The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed. PMID:27331413

  14. pH dependence of Fenton reagent generation and As(III) oxidation and removal by corrosion of zero valent iron in aerated water.

    PubMed

    Katsoyiannis, Ioannis A; Ruettimann, Thomas; Hug, Stephan J

    2008-10-01

    Corrosion of zerovalent iron (ZVI) in oxygen-containing water produces reactive intermediates that can oxidize various organic and inorganic compounds. We investigated the kinetics and mechanism of Fenton reagent generation and As(III) oxidation and removal by ZVI (0.1m2/g) from pH 3-11 in aerated water. Observed half-lives for the oxidation of initially 500 microg/L As(III) by 150 mg Fe(0)/L were 26-80 min at pH 3-9. At pH 11, no As(III) oxidation was observed during the first two hours. Dissolved Fe(III) reached 325, 140, and 6 microM at pH 3, 5, and 7. H2O2 concentrations peaked within 10 min at 1.2, 0.4, and < 0.1 microM at pH 3, 5, and 7, and then decreased to undetectable levels. Addition of 2,2'-bipyridine (1-3 mM), prevented Fe(II) oxidation by O2 and H2O2 and inhibited As(III)oxidation. 2-propanol (14 mM), scavenging OH-radicals, quenched the As(III) oxidation at pH 3, but had almost no effect at pH 5 and 7. Experimental data and kinetic modeling suggest that As(III) was oxidized mainly in solution by the Fenton reaction and removed by sorption on newly formed hydrous ferric oxides. OH-radials are the main oxidant for As(III) at low pH, whereas a more selective oxidant oxidizes As(III) at circumneutral pH. PMID:18939581

  15. USING ZERO-VALENT METAL NANOPARTICLES TO REMEDIATE ORGANIC CONTAMINANTS

    EPA Science Inventory

    The transport of organic contaminants down the soil profile constitutes a serious threat to the quality of ground water. Zero-valent metals are considered innocuous abiotic agents capable of mediating decontamination processes in terrestrial systems. In this investigation, ze...

  16. Study of different methods for enhancing the nitrate removal efficiency of a zero-valent metal process.

    PubMed

    Cheng, S F; Huang, C Y; Liu, J Y

    2006-01-01

    This study explores the effect of several enhancing methods, namely acid wash pretreatment, ultrasound treatment and addition of nickel catalyst on the nitrate removal efficiency of three zero-valent metals--iron, aluminium and zinc. It is hoped that by learning about the major reaction pathways of nitrate removal with zero-valent metals and the main factors influencing the reactivity of those zero-valent metals, optimum process conditions may be identified. The study results show that direct transfer of electrons is the major reaction pathway. Thus increasing a clean, fresh metal surface and decreasing the thickness of the diffusion layer to accelerate mass transfer are the main determinants of reaction rate. In the absence of a clean, fresh metal surface, the catalytic reaction of nickel becomes the primary removal pathway. PMID:16862777

  17. Dechlorination of perchloroethylene using zero-valent metal and microbial community

    NASA Astrophysics Data System (ADS)

    Ma, Changwen; Wu, Yanqing

    2008-07-01

    This research evaluates an integrated technique for the degradation of perchloroethylene (PCE) using a combination of zero-valent metal and an anaerobic microbial community. The microbial community was obtained from river sediment through a series of cultivation and enrichment processes, and was able to successfully convert PCE to ethylene. The degradation tests were carried out in five groups of reactors, i.e. Zn (zero-valent zinc), Fe (zero-valent iron), MB (a microbial community), ZnMB (zinc and a microbial community) and FeMB (iron and a microbial community). The results suggested that the FeMB system had the highest efficiency in removing PCE (about 99.9% after 24 days), followed by Zn (98.5%), ZnMB (84.8%), Fe (76.9%) and MB (49.6%). The degradation kinetics of PCE could be described by a pseudo-first-order reaction; the apparent reaction rate constants were 0.231, 0.187, 0.135, 0.076, 0.031 days-1 for the Zn, FeMB, ZnMB, Fe, and MB systems, respectively. Much more Cl- was detected as a by-product in the degradation tests using FeMB or ZnMB than using Fe or Zn. The results implied that not only PCE, but also the reaction intermediates, e.g., trichloroethylene (TCE) and dichloroethylenes (DCE isomers) may have been dechlorinated in the FeMB and ZnMB systems. Results suggest that the presence of the microbial community in the FeMB and ZnMB systems may not only affect the removal efficiency of PCE, but can also change the reaction pathways in the dechlorination process. The integrated technique combining the iron and the microbial community showed better degradation efficiency than the others; it may be viewed as an environmentally desirable remediation.

  18. Zero-valent and charged metals combined with anaerobic bacteria in methanogenesis

    SciTech Connect

    Sysak, J.C.

    1995-12-31

    Zero-valent iron has been observed to effect the decomposition of alkyl and aromatic halides with the reduction to the corresponding hydrocarbon. The reaction is of interest in conjunction with bioredmediation of soil contaminated with CHCl{sub 3} and other environmentally sensitive halides. This work examines the effects of anaerobic bacteria in conjunction with various metals on the methanogenesis of pollutants as well as biomass of various types. The results of the addition of Ni{sup 2+} to the methyl coenzyme M reductase system was investigated and the results presented involving a number of bacterial species in addition to a mixed sewage culture immaculate.

  19. 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. PMID:18166266

  20. Reductive elimination of chlorinated ethylenes by zero-valent metals

    SciTech Connect

    Roberts, A.L.; Totten, L.A.; Arnold, W.A.; Burris, D.R.; Campbell, T.J.

    1996-08-01

    To date it does not appear to have been demonstrated in the literature that halogenated ethylenes can undergo reductive {beta}-elimination to alkynes under environmental conditions. The purpose of this paper is to provide experimental evidence that such pathways may be involved in the reaction of chloroethylenes with zero-valent metals as well as to speculate on the significance of the products that may result. Calculations indicate that reductive {beta}-elimination reactions of chloroethylenes are in fact comparable energetically to hydrogenolysis at neutral pH. Experiments were therefore initiated to assess whether {beta}-elimination reactions of chlorinated ethylenes could occur in the presence of two zero-valent metals, Fe and Zn. 76 refs., 3 figs., 1 tab.

  1. Reduction of concentrated nitrate by using in situ synthesized zero-valent copper.

    PubMed

    Belay, Tihitinna Asmellash; Lin, F M; Lin, C Y; Hsiao, H M; Chang, M F; Liu, J C

    2015-01-01

    Although zero-valent iron represents a promising approach for reduction of nitrate (NO(3)(-)) in water, its application in concentrated nitrate is limited by surface passivation. In this study, an alternative approach using in situ synthesized zero-valent copper (Cu(0)) produced by borohydride (NaBH(4)) was investigated. Complete reduction was observed within 55 min by reacting 677 mg-N/L of NO(3)(-) with CuO (0.312 g/L) and NaBH(4) (4.16 g/L) at 60 °C. The pseudo-first-order rate constant was 0.059 min(-1), and it increased threefold when the CuO dose was increased to 1.24 g/L. Increasing the NaBH(4) dose produced less nitrite (NO(2)(-)) throughout the experiments, indicating that it is the primary agent for reducing NO(2)(-). The initial pH exerted a significant effect on the reaction rate, and NO(3)(-) was rapidly reduced when the initial pH was less than 4. Based on the research findings, possible reaction pathways for NO(3)(-) reduction by Cu(0) are proposed in this work. PMID:26360756

  2. FINAL REPORT. FUNDAMENTAL STUDIES OF THE REMOVAL OF CONTAMINANTS FROM GROUND AND WASTE WATER VIA REDUCTION BY ZERO-VALENT METALS

    EPA Science Inventory

    Oxyanions of uranium, selenium, chromium, arsenic, technetium, and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites, and in other areas of the U.S. A potential remediation method is to react the contaminated water with zero-valent iron (ZVI). We ar...

  3. Partial oxidation (“aging”) and surface modification decrease the toxicity of nano-sized zero valent iron     

    EPA Science Inventory

    Zero-valent iron (nZVI) is a redox-active nanomaterial used for in situ remediation of contaminated groundwater. To assess the effect of “aging” and surface modification on its potential neurotoxicity, cultured rodent microglia and neurons were exposed to fresh nZVI, “aged” (>11...

  4. Emplacement of zero-valent metal for remediation of deep contaminant plumes

    SciTech Connect

    Hubble, D.W.; Gillham, R.W.; Cherry, J.A.

    1997-12-31

    Some groundwater plumes containing chlorinated solvent contaminants are found to be so deep that current in situ remediation technologies cannot be economically applied. Also, source zones are often found to be too deep for removal or inaccessible due to surface features. Plumes emanating from these sources require containment or treatment. Containment technologies are available for shallow sites (< 15 m) and are being developed for greater depths. However, it is important to advance the science of reactive treatment - both for cut off of plumes and to contain and treat source zones. Zero-valent metal technology has been used for remediation of solvent plumes at sites in Canada, the UK and at several industrial and military sites in the USA. To date, all of the plumes treated with zero-valent metal (granular iron) have been at depths less than 15 m. This paper gives preliminary results of research into methods to emplace granular iron at depths in the range of 15 to 60 m. The study included review of available and emerging methods of installing barrier or reactive material and the selection, preliminary design and costing of several methods. The design of a treatment system for a 122 m wide PCE plume that, immediately down gradient from its source, extends from a depth of 24 to 37 m below the ground surface is used as a demonstration site. Both Permeable Reactive Wall and Funnel-and-Gate{trademark} systems were considered. The emplacement methods selected for preliminary design and costing were slurry wall, driven/vibrated beam, deep soil mixing and hydrofracturing injection. For each of these methods, the iron must be slurried for ease of pumping and placement using biodegradable polymer viscosifiers that leave the iron reactive.

  5. Reaction of 1,1,1-trichloroethane with zero-valent metals and bimetallic reductants

    SciTech Connect

    Fennelly, J.P.; Roberts, A.L.

    1998-07-01

    Information concerning the pathways and products of reaction of 1,1,1-trichloroethane (1,1,1-TCA) with zero-valent metals may be critical to the success of in situ treatment techniques. Many researchers assume that alkyl polyhalides undergo reduction via stepwise hydrogenolysis (replacement of halogen by hydrogen). Accordingly, 1,1,1-TCA should react to 1,1-dichloroethane (1,1-DCA), to chloroethane, and finally to ethane. Experiments conducted in laboratory-scale batch reactors indicate, however, that with zinc, iron, and two bimetallic reductants (nickel-plated iron and copper-plated iron) this simplistic stepwise scheme cannot explain observed results. 1,1,1-TCA was found to react rapidly with zinc to form ethane and 1,1-DCA. Independent experiments confirmed that 1,1-DCA reacts too slowly to represent an intermediate in the formation of ethane. In reactions with iron, nickel/iron, and copper/iron, cis-2-butene, ethylene, and 2-butyne were also observed as minor products. Product ratios were dependent on the identity of the metal or bimetallic reductant, with zinc resulting in the lowest yield of chlorinated product. For reactions with iron and bimetallic reductants, a scheme involving successive one-electron reduction steps to form radicals and carbenoids can be invoked to explain the absence of observable intermediates, as well as the formation of products originating from radical or possibly from carbenoid coupling.

  6. Fundamental Studies of The Removal of Contaminants from Ground and Waste Waters Via Reduction By Zero-Valent metals

    SciTech Connect

    Jory A. Yarmoff; Christopher Amrhein

    2002-04-23

    Oxyanions of uranium, selenium, chromium, arsenic, technetium, and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites, and in other areas of the U.S.. A potential remediation method is to react the contaminated water with zero-valent iron (ZVI). We are performing fundamental investigations of the interactions of the relevant compounds with Fe filings and single- and poly-crystalline surfaces. The aim of this work is to develop the physical and chemical understanding that is necessary for the development of cleanup techniques and procedures.

  7. ZERO-VALENT IRON PRB APPLICATION EXPANDS TO ARSENIC REMOVAL

    EPA Science Inventory

    The U.S. EPA Office of Research and Development’s National Risk Management Research Laboratory (NRMRL) and Region 8 have begun evaluating performance of a pilot-scale permeable reactive barrier (PRB) to treat arsenic-contaminated ground water at the ASARCO Superfund near Helena, ...

  8. Mitigation of Irrigation Water Using Zero-Valent Iron Treatment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Significant problems have occurred in the U.S. with regard to the contamination of produce by pathogenic bacteria. Minimally processed produce lacks the processing and preparation hurdles, such as cooking, to aid in reduction or elimination of the occasional and incidental contamination that can le...

  9. FUNDAMENTAL STUDIES OF THE REMOVAL OF CONTAMINANTS FROM GROUND AND WASTE WATERS VIA REDUCTION BY ZERO-VALENT METALS

    SciTech Connect

    Yarmoff, Jory A.; Amrhein, Christopher

    2000-06-01

    Oxyanions of uranium, selenium, chromium, arsenic, technetium, and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites. A potential remediation method is to react the contaminated water with zero-valent iron (ZVI). In this reaction, the iron serves as both an electron source and as a catalyst. Elemental iron is already being used on an experimental basis at many sites. Both in situ reactive barriers and above-ground reactors are being developed and field tested at this time. However, the design and operation of these treatment systems requires a detailed process-level understanding of the interactions between the contaminants and the iron surfaces. We are performing fundamental investigations of the interactions of the relevant compounds with Fe filings and single- and poly-crystalline surfaces. The aim of this work is to develop the fundamental physical and chemical understanding that is necessary for the development of cleanup techniques and procedures.

  10. Formation of hydrocarbons from the reduction of aqueous CO{sub 2} by zero-valent metal

    SciTech Connect

    Hardy, L.I.; Gillham, R.W.

    1995-12-01

    The reduction of aqueous CO{sub 2} by zero-valent iron was studied in batch and column experiments. Ten hydrocarbons up to C5 were identified as products of the reduction process and were shown to have Anderson-Schultz-Flory (ASF) product distributions. A direct consequence of the ASF product distribution is that a significant mass of hydrophobic hydrocarbons may remain attached to the iron surface. The slow desorption of these products may become the rate-limiting step in dehalogenation of chlorinated organics. Based on a reaction mechanism proposed for the electro-reduction of aqueous CO{sub 2} with nickel electrodes, iron acts as both a reactant, by corroding to supply electrons, and as a catalyst by promoting the formation and growth of hydrocarbon chains. Water is also a reactant in the system.

  11. Reduction of N-nitrosodimethylamine with zero-valent zinc.

    PubMed

    Han, Ying; Chen, Zhong-lin; Tong, Li-na; Yang, Lei; Shen, Ji-min; Wang, Bin-yuan; Liu, Yue; Liu, Yu; Chen, Qian

    2013-01-01

    N-Nitrosodimethylamine (NDMA) is known as the disinfection by-product and the pollutant in the source water. Reduction with zero-valent zinc (Zn(0)) was investigated as a potential technology to treat NDMA. The results showed that Zn(0) was effective for NDMA reduction at initial pH 7.0. There were lag period and rapid period during the process, the corresponding zero-order rate constant (k(zero)) was 2.968 ± 0.245 μg L(-1) h(-1) ([Zn(0)](0) = 10g L(-1)),the mass normalized pseudo-first-order rate (k(M)) was 0.1215 ± 0.0171 L g(-1) h(-1). The reactivity of zinc on NDMA removal was consistent with the zinc corrosion rate. NDMA had little effect on the corrosion of zinc. Lower solution pH benefited the reduction of NDMA with Zn(0). The consumption of the oxygen and the localized acidification should be the cause of the shift from lag to rapid reaction period in the aerobic experiments. 1,1-dimethylhydrazine (unsymmetrical dimethylhydrazine, UDMH), dimethylamine (DMA) were detected as the products of NDMA degradation. The nitrogen mass balance at 24 h was 56%, the loss can be due to the formation of ammonium, the degradation of UDMH and other unmeasured products. DMA formed during the degradation of UDMH with Zn(0), the nitrogen loss could be caused by the formation of unmeasured products. Catalytic hydrogenation is proposed to be the mechanism based on the results and the redox properties of zinc and NDMA. One reduction process is: the active hydrogen atoms initially cleave and reduce the N=O bond in NDMA, generating UDMH. Then the N-N bond in UDMH is cleaved to form DMA and ammonium. PMID:23084118

  12. The experimental study of Cr6+ contaminated water remediation by zero-valent nano-Fe

    NASA Astrophysics Data System (ADS)

    Sun, X. N.; Liu, A. P.; Chen, Q. F.; Wang, X.

    2015-09-01

    In recent years, researchers have developed a number of new types of zero-valent nano-Fe remediation materials applied in the remediation of contaminated soil and water, which has attracted wide attentions. This paper selected soil leaching wastewater severely contaminated by chromium as target of the study and chose zero-valent nano-Fe, Na2SO3 and NaHSO3 for comparison experiments to study the effects on removing Cr6+ under experimental conditions of different pH values, dosages and reaction times. As is shown in the experiments, zero-valent nano-Fe has the highest removal rates for Cr6+, while the reaction of Na2SO3 is the slowest under the same conditions. However, both removal rates are prone to be stable after 10 min. Dosages do not make a distinct difference and the pH value has the least effect on the repair of zero-valent nano-Fe.

  13. Competing TCE and cis-DCE degradation kinetics by zero-valent iron—experimental results and numerical simulation

    NASA Astrophysics Data System (ADS)

    Schäfer, Dirk; Köber, Ralf; Dahmke, Andreas

    2003-09-01

    The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Schäfer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of

  14. Zero-Valent Metallic Treatment System and Its Application for Removal and Remediation of Polychlorinated Biphenyls (Pcbs)

    NASA Technical Reports Server (NTRS)

    Quinn, Jacqueline W. (Inventor); Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor); Brooks, Kathleen B. (Inventor)

    2012-01-01

    PCBs are removed from contaminated media using a treatment system including zero-valent metal particles and an organic hydrogen donating solvent. The treatment system may include a weak acid in order to eliminate the need for a coating of catalytic noble metal on the zero-valent metal particles. If catalyzed zero-valent metal particles are used, the treatment system may include an organic hydrogen donating solvent that is a non-water solvent. The treatment system may be provided as a "paste-like" system that is preferably applied to natural media and ex-situ structures to eliminate PCBs.

  15. Fundamental Studies of the Removal of Contaminants from Ground and Waste Waters via Reduction by Zero-Valent Metals

    SciTech Connect

    Yarmoff, Jory A.; Amrhein, Christopher

    1999-06-01

    Contaminated groundwater and surface waters are a problem throughout the United States and the world. In many instances, the types of contamination can be directly attributed to man's actions. For instance, the burial of chemical wastes, casual disposal of solvents in unlined pits, and the development of irrigated agriculture have all contributed to groundwater and surface water contamination. The kinds of contaminants include chlorinated solvents and toxic trace elements (including radioisotopes) that are soluble and mobile in soils and aquifers. Oxyanions of uranium, selenium, chromium, arsenic, technetium, and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites. Uranium is a particularly widespread contaminant at most DOE sites including Oak Ridge, Rocky Flats, Hanford, Idaho (INEEL), and Fernald. The uranium contamination is associated with mining and milling of uranium ore (UMTRA sites), isotope separation and enrichment, and mixed waste and TRU waste burial. In addition, the careless disposal of halogenated solvents, such as carbon tetrachloride and trichloroethylene, has further contaminated many groundwaters at these sites. A potential remediation method for many of these oxyanions and chlorinated-solvents is to react the contaminated water with zero-valent iron. In this reaction, the iron serves as both an electron source and as a catalyst. Elemental iron is already being used on an experimental basis at many DOE sites. Both in situ reactive barriers and above-ground reactors are being developed for this purpose. However, the design and operation of these treatment systems requires a detailed process-level understanding of the interactions between the contaminants and the iron surfaces. We are performing fundamental investigations of the interactions of the relevant chlorinated solvents and trace element-containing compounds with single- and poly-crystalline Fe surfaces. The aim of this work is to develop th e fundamental

  16. Nanoscale zero valent supported by Zeolite and Montmorillonite: Template effect of the removal of lead ion from an aqueous solution.

    PubMed

    Arancibia-Miranda, Nicolás; Baltazar, Samuel E; García, Alejandra; Muñoz-Lira, Daniela; Sepúlveda, Pamela; Rubio, María A; Altbir, Dora

    2016-01-15

    In this work, we have studied the Pb(2+) sorption capacity of Zeolite (Z) and Montmorillonite (Mt) functionalized with nanoscale zero-valent iron (nZVI), at 50% w/w, obtained by means of an impregnating process with a solvent excess. The composites were characterized by several techniques including X-ray diffraction; scanning electron microscopy (SEM); BET area; isoelectric point (IEP); and, finally a magnetic response. Comparatively significant differences in terms of electrophoretic and magnetic characteristics were found between the pristine materials and the composites. Both structures show a high efficiency and velocity in the removal of Pb(2+) up to 99.0% (200.0 ppm) after 40 min of reaction time. The removal kinetics of Pb(2+) is adequately described by the pseudo second-order kinetic model, and the maximum adsorbed amounts (q(e)) of this analyte are in close accordance with the experimental results. The intraparticle diffusion model shows that this is not the only rate-limiting step, this being the Langmuir model which was well adjusted to our experimental data. Therefore, maximum sorption capacities were found to be 115.1±11.0, 105.5±9.0, 68.3±1.3, 54.2±1.3, and 50.3±4.2 mg g(-1), for Mt-nZVI, Z-nZVI, Zeolite, Mt, and nZVI, respectively. The higher sorption capacities can be attributed to the synergetic behavior between the clay and iron nanoparticles, as a consequence of the clay coating process with nZVI. These results suggest that both composites could be used as an efficient adsorbent for the removal of lead from contaminated water sources. PMID:26384998

  17. Cryptic Role of Zero-Valent Sulfur in Metal and Metalloid Geochemistry in Euxinic Waters

    NASA Astrophysics Data System (ADS)

    Helz, G. R.

    2014-12-01

    Natural waters that are isolated from the atmosphere in confined aquifers, euxinic basins and sediment pore waters often become sulfidic. These waters are conventionally described simply as reducing environments. But because nature does not constrain their exposure to reducing equivalents (e.g. from organic matter) and oxidizing equivalents (e.g. from Fe,Mn oxides), these reducing environments in fact vary cryptically in their redox characteristics. The implications for trace metal and metalloid cycles are only beginning to be explored. The activity of zero-valent sulfur (aS0), a virtual thermodynamic property, is a potentially useful index for describing this variation. At a particular temperature and ionic strength, aS0 can be quantified from knowledge of pH and the total S(0) to total S(-II) ratio. Although data are incomplete, the deep waters of the Black Sea (aS0 ca. 0.3) appear to be more reducing than the deep waters of the Cariaco Basin (aS0 ca. 0.5) even though both are perennially sulfidic. An apparent manifestation is a greater preponderance of greigite relative to mackinawite in the Cariaco Basin. Interestingly, greigite is stable relative to mackinawite in both basins but predominates only at the higher aS0. Values of aS0 in sulfidic natural waters span the range over which Hg-polysulfide complexes gain predominance over Hg sulfide complexes. Competition between these ligands is thought to influence biological methylation, mercury's route into aquatic and human food chains. In sulfidic deep ground waters, the redox state and consequent mobility of As, a global human hazard, will depend on aS0. At intermediate sulfide concentrations, higher aS0 favors more highly charged and thus less mobile As(V) species relative to As(III) species despite the overall reducing characteristics of such waters. Helz, G.R. (2014) Activity of zero-valent sulfur in sulfidic natural waters. Geochem. Trans. In press.

  18. Oxidative removal of bisphenol A using zero valent aluminum-acid system.

    PubMed

    Liu, Wanpeng; Zhang, Honghua; Cao, Beipei; Lin, Kunde; Gan, Jay

    2011-02-01

    Bisphenol A (BPA), a controversial endocrine disruptor, is ubiquitous in the aquatic environment. In this study, the oxidative degradation of BPA and its mechanism using zero valent aluminum (ZVAl)-acid system under air-equilibrated conditions was investigated. Under pH <3.5 acidic conditions, ZVAl demonstrated an excellent capacity to remove BPA. More than 75% of BPA was eliminated within 12 h in pH 1.5 reaction solutions initially containing 4.0 g/L aluminum and 2.0 mg/L BPA at 25 ± 1 °C. The removal of BPA was further accelerated with increasing aluminum loadings. Higher temperature and lower initial pH also facilitated BPA removal. The addition of Fe(2+) into the ZVAl-acid system significantly accelerated the reaction likely due to the enhancing transformation of H(2)O(2) to HO via Fenton reaction. Furthermore, the primary products or intermediates including monohydroxylated BPA, hydroquinone, 2-(4-hydroxyphenyl)propane and 4-isopropenylphenol, were identified and a possible reaction scheme was proposed. The remarkable capacity of the ZVAl-acid system in removing BPA displays its potential application in the treatment of organic compound-contaminated water. PMID:21185583

  19. Photocatalysis using zero-valent nano-copper for degrading methyl orange under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Liú, Dan; Wang, Guoqiang; Liŭ, Dan; Lin, Junhong; He, Yingqiao; Li, Xiangru; Li, Ziheng

    2016-03-01

    As one of zero-valent transition metals, nano-copper was synthesized by a simple chemical reduction route and its photocatalytic activity was appraised by the degradation rate of methyl orange (MO) in aqueous solution under irradiation of a three-band fluorescent lamp. The results showed that nano-copper possessed visible-light photocatalytic activity. The finite-difference time-domain (FDTD) method was used to simulate the electric field distribution of nano-copper. From the results of simulation, it found that there was an enhancement electric field in course of light absorption on the surface of nano-copper, different morphology resulted in a diverse electric field distribution. Enhancement electric field intensity decided the visible-light photocatalytic activity of nano-copper. So the activity was affected by the morphology of nano-copper, as the size reduced and surface roughness increased, could be enhanced. It did be worth noting that the nanoscale of copper played the fatal decisive role for whether copper has the ability to degrade MO. So As-prepared nano-copper may be a novel visible-light photocatalytic material to treat organic pollution.

  20. Neutral zero-valent s-block complexes with strong multiple bonding.

    PubMed

    Arrowsmith, Merle; Braunschweig, Holger; Celik, Mehmet Ali; Dellermann, Theresa; Dewhurst, Rian D; Ewing, William C; Hammond, Kai; Kramer, Thomas; Krummenacher, Ivo; Mies, Jan; Radacki, Krzysztof; Schuster, Julia K

    2016-07-01

    The metals of the s block of the periodic table are well known to be exceptional electron donors, and the vast majority of their molecular complexes therefore contain these metals in their fully oxidized form. Low-valent main-group compounds have recently become desirable synthetic targets owing to their interesting reactivities, sometimes on a par with those of transition-metal complexes. In this work, we used stabilizing cyclic (alkyl)(amino)carbene ligands to isolate and characterize the first neutral compounds that contain a zero-valent s-block metal, beryllium. These brightly coloured complexes display very short beryllium-carbon bond lengths and linear beryllium coordination geometries, indicative of strong multiple Be-C bonding. Structural, spectroscopic and theoretical results show that the complexes adopt a closed-shell singlet configuration with a Be(0) metal centre. The surprising stability of the molecule can be ascribed to an unusually strong three-centre two-electron π bond across the C-Be-C unit. PMID:27334631

  1. Aerosol synthesis of nano and micro-scale zero valent metal particles from oxide precursors

    SciTech Connect

    Phillips, Jonathan; Luhrs, Claudia; Lesman, Zayd; Soliman, Haytham; Zea, Hugo

    2010-01-01

    In this work a novel aerosol method, derived form the batch Reduction/Expansion Synthesis (RES) method, for production of nano / micro-scale metal particles from oxides and hydroxides is presented. In the Aerosol-RES (A-RES) method, an aerosol, consisting of a physical mixture of urea and metal oxide or hydroxides, is passed through a heated oven (1000 C) with a residence time of the order of 1 second, producing pure (zero valent) metal particles. It appears that the process is flexible regarding metal or alloy identity, allows control of particle size and can be readily scaled to very large throughput. Current work is focused on creating nanoparticles of metal and metal alloy using this method. Although this is primarily a report on observations, some key elements of the chemistry are clear. In particular, the reducing species produced by urea decomposition are the primary agents responsible for reduction of oxides and hydroxides to metal. It is also likely that the rapid expansion that takes place when solid/liquid urea decomposes to form gas species influences the final morphology of the particles.

  2. Reaction of zero-valent magnesium with water: Potential applications in environmental remediation

    NASA Astrophysics Data System (ADS)

    Lee, Giehyeon; Park, Jaeseon

    2013-02-01

    This study examined the dissolution kinetics of granular zero-valent Mg (ZVMg) at pH 7 in water that was open to the atmosphere and buffered with 50 mM Na-MOPS. The oxidative dissolution of ZVMg was rapid; the initial amount of ZVMg (10-50 mg/L) dissolved completely within 200 min. The rate and extent of ZVMg dissolution was not affected by atmospheric oxygen. Although the oxidation of ZVMg is thermodynamically more feasible by dissolved oxygen or proton ions (H+), the primary oxidants are water molecules. The initial rate of ZVMg dissolution obeys first order kinetics with respect to ZVMg concentration with an observed rate constant, kMg,7 = 1.05 ± 0.06 × 10-2 min-1. Model calculations using the rate constant perfectly predict the extent of ZVMg dissolution for an extended time period at lower [Mg0]0 but underestimate at 50 mg/L [Mg0]0. The offset is likely attributed to the rapid dissolution of ZVMg particles, which could cause a substantial increase in the specific surface area. As to the reactivity of Mg-water system, we suggest that the hydrated electron (eaq-), the most powerful reducing agent, would probably be the major reactive entity under neutral and alkaline conditions. In addition, we discuss briefly the factors affecting the rate and extent of the Mg-water reaction such as background electrolytes, ZVMg impurities, surface passivation, solution pH and temperature based on literature review.

  3. LABORATORY EVALUATION OF ZERO-VALENT IRON TO TREAT GROUNDWATER IMPACTED BY ACID MINE DRAINAGE

    EPA Science Inventory

    The generation and release of acidic, metal-rich water from mine wastes continues to be an intractable environmental problem. Although the effects of acid mine drainage (AMD) are most evident in surface waters, there is an obvious need for developing cost-effective approaches fo...

  4. Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: A field investigation

    NASA Astrophysics Data System (ADS)

    Liang, Liyuan; Moline, Gerilynn R.; Kamolpornwijit, Wiwat; West, Olivia R.

    2005-08-01

    Geochemical and mineralogical changes were evaluated at a field Fe 0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO 3- groundwater. In the 5-year study period, the Fe 0 remained reactive as shown in pore-water monitoring data, where increases in pH and the removal of certain ionic species persisted. However, coring revealed varying degrees of cementation. After 3.8-year treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe 0 interface. Elsewhere, Fe 0 filings were loose with some cementation. Fe 0 corrosion and pore volume reduction at this site are more severe due to the presence of NO 3- at a high level. Tracer tests indicate that hydraulic performance deteriorated: the flow distribution was heterogeneous and under the influence of interfacial cementation a large portion of water was diverted around the Fe 0 and transported outside the PRB. Based on the equilibrium reductions of NO 3- and SO 42- by Fe 0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 years of operation. Additionally, modeling showed a spatial distribution of mineral precipitate volumes, with the maximum advancing from the interface toward downgradient with time. This study suggests that water quality monitoring, coupled with hydraulic monitoring and geochemical modeling, can provide a low-cost method for assessing PRB performance.

  5. MINERAL PARAGENESIS OF FINE-GRAINED PRECIPITATES IN PERMEABLE REACTIVE BARRIERS OF ZERO-VALENT IRON

    EPA Science Inventory

    U.S. EPA (Environmental Protection Agency) staff developed a field procedure to measure hydraulic conductivity using a direct-push system to obtain vertical profiles of hydraulic conductivity. Vertical profiles were obtained using an in situ field device-composed of a
    Geopr...

  6. Efficient transformation of DDTs with Persulfate Activation by Zero-valent Iron Nanoparticles: A Mechanistic Study.

    PubMed

    Zhu, Changyin; Fang, Guodong; Dionysiou, Dionysios D; Liu, Cun; Gao, Juan; Qin, Wenxiu; Zhou, Dongmei

    2016-10-01

    In this study, persulfate (PS) activation by nano-Fe(0) was used to degrade dichlorodiphenyltrichloroethane (DDT), and the mechanism of this process was elucidated with EPR, GC-MS and free-radical quenching studies. It was found that DDT was degraded efficiently in PS/nano-Fe(0), and GC-MS analysis showed that benzoic acid, benzyl alcohol, dichlorobenzophenone and 2,2-bis(p-chlorophenyl)-ethane were the dominant products of DDT degradation, while only dechlorination products (DDD and DDE) were observed in nano-Fe(0) without persulfate. EPR results showed that persulfate activation by nano-Fe(0) led to the production of more sulfate radicals and hydroxyl radicals, which accounted for DDT degradation. But the free radical quenching studies suggested that the addition of ethanol to PS/nano-Fe(0) favored the reductive dechlorination of DDT, which was ascribed that the formed ethanol radical (CH(CH3)OH) enhanced the reductive dechlorination of DDT. Furthermore, the nano-Fe(0) loading not only affected the degradation efficiency of DDT, but also influenced the intermediate product distribution of DDT degradation in the PS/nano-Fe(0) process. PMID:27236432

  7. Assessment of polyphenol coated nano zero valent iron for hexavalent chromium removal from contaminated waters.

    PubMed

    Mystrioti, C; Sparis, D; Papasiopi, N; Xenidis, A; Dermatas, D; Chrysochoou, M

    2015-03-01

    Alternative plant extracts were examined as raw materials for the synthesis of nZVI from ferric solutions. Four plants were selected for evaluation, i.e. Camellia sinensis (green tea, GT), Syzygium aromaticum (clove, CL), Mentha spicata (spearmint, SM) and Punica granatum (pomegranate, PG). Based on the results obtained, it was concluded that the reduction of Fe(III) with the herb extracts is not complete. Using the GT extract, approximately 28 mM of the initial 66 mM of Fe (42.4 %) are reduced to the elemental state Fe(0). The highest reduction of Fe(III), about 53 %, was achieved with PG and the lowest, only 15.6 %, with the SM extract. Additional batch experiments have been carried out to evaluate the effectiveness of nZVI, synthesized with GT, CL, SM and PG, for the removal of hexavalent chromium from a 0.96 mM solution. The highest reduction of Cr(VI) (96 %) was obtained using the nZVI suspension produced with PG juice. The other three nZVI suspensions, i.e. CL-nZVI, GT-nZVI, and SM-nZVI, had a comparable effectiveness corresponding to 70 % reduction of chromate. PMID:25512186

  8. Effects of zero-valent metals together with quartz sand on the mechanochemical destruction of dechlorane plus coground in a planetary ball mill.

    PubMed

    Wang, Haizhu; Huang, Jun; Zhang, Kunlun; Yu, Yunfei; Liu, Kai; Yu, Gang; Deng, Shubo; Wang, Bin

    2014-01-15

    Mechanochemical destruction by grinding with additives in high energy ball milling has been identified as a good alternative to traditional incineration for the disposal of wastes containing halogenated organic pollutants. Despite CaO normally used as an additive, recently Fe+SiO2 has been used to replace CaO for a faster destruction. In the present study, zero-valent metals (Al, Zn, besides Fe) together with SiO2 were investigated for their efficiencies of prompting the destruction of dechlorane plus (DP). Aluminum was found of be the best with a destruction percentage of nearly 99% for either syn- or anti-DP after 2.5h milling. In comparison, only 88/85% and 37/32% of syn-/anti-DP were destroyed when using zinc and iron after the same time, respectively. The detected water soluble chloride was lower than the stoichiometric amount containing in the original DP samples, due to the Si-Cl bond formed during the process. The potential fate of C and Cl present in DP is in the form of inorganic carbon, inorganic Cl and formation of Si-Cl bonds, respectively. The results suggested that Al+SiO2 is promising in the mechanochemical destruction of chlorinated organic pollutants like DP. PMID:24295775

  9. Evaluating Trichloroethylene Degradation Using Differing Nano- and Micro-Scale Iron Particles

    NASA Technical Reports Server (NTRS)

    Berger, Cristina M.; Geiger, Cherie L.; Clausen, Christian A.; Billow, Alexa M.; Quinn, Jacqueline W.; Brooks, Kathleen B.

    2006-01-01

    Trichioroethylene, or TCE, is a central nervous system depressant and possible carcinogen, as well as a persistent groundwater pollutant. TCE exists in the aquifer either as free product in the form of a dense non-aqueous phase liquid (DNAPL) or as a dissolved-phase constituent. It is only slightly soluble in water, so dissolution of the contaminant is a long-term process and in-situ remediation is difficult. To remedy this, NASA and the University of Central Florida developed Emulsified Zero-Valent Iron, or EZVI. The emulsion droplet contains ZVI particles and water encapsulated by an oil/surfactant membrane, and effectively penetrates to degrade DNAPL-phase TCE. To maximize the efficiency of this process, several commercially available ZVIs of radically different particle sizes and morphologies both in emulsion and as neat (unemulsified) metal were evaluated for relative effectiveness at TCE degradation.

  10. Fundamental studies of the removal of contaminants from ground and waste waters via reduction by zero-valent metals. 1998 annual progress report

    SciTech Connect

    Yarmoff, J.A.; Amrhein, C.

    1998-06-01

    'Contaminated groundwater and surface waters are a problem throughout the US and the world. In many instances, the types of contamination can be directly attributed to man''s actions. For instance, the burial of wastes, casual disposal of solvents in unlined pits, and the development of irrigated agriculture have all contributed to groundwater and surface water contamination. The kinds of contaminants include chlorinated solvents and toxic trace elements that are soluble and mobile in soils and aquifers. Oxyanions of selenium, chromium, uranium, arsenic, and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites. In addition, the careless disposal of cleaning solvents, such as carbon tetrachloride and trichloroethylene, has further contaminated many groundwaters at these sites. Oxyanions of selenium, nitrogen, arsenic, vanadium, uranium, chromium, and molybdenum are contaminants in agricultural areas of the Western US. The management of these waters requires treatment to remove the contaminants before reuse or surface water disposal. In one instance in the Central Valley of California, the discharge of selenate-contaminated shallow groundwater to a wildlife refuge caused catastrophic bird deaths and deformities of embryos. A potential remediation method for many of these oxyanions and chlorinated-solvents is to react the contaminated water with zero-valent iron. In this reaction, the iron serves as both an electron source and as a catalyst. Elemental iron is already being used on an experimental basis. Both in-situ reactive barriers and above-ground reactors are being developed for this purpose. However, the design and operation of these treatment systems requires a detailed process-level understanding of the interactions between the contaminants and the iron surfaces. Only limited success has been achieved in the field, partly because the basic surface chemical reactions are not well understood. The authors are performing fundamental

  11. Recovery of copper as zero-valent phase and/or copper oxide nanoparticles from wastewater by ferritization.

    PubMed

    Heuss-Aßbichler, Soraya; John, Melanie; Klapper, Daniel; Bläß, Ulrich W; Kochetov, Gennadii

    2016-10-01

    Recently the focus of interest changed from merely purification of the waste water to recover heavy metals. With the slightly modified ferritization process presented here it is possible to decrease initial Cu(2+) concentrations up to 10 g/l to values <0.3 mg/l. The recovery rates of copper of all experiments are in the rage of 99.98 to almost 100%. Copper can be precipitated as oxide or zero valent metal (almost) free of hydroxide. All precipitates are exclusively of nanoparticle size. The phase assemblage depends strongly on experimental conditions as e.g. reaction temperature, pH-value, initial concentration and ageing time and condition. Three different options were developed depending on the reaction conditions. Option 1.) copper incorporation into the ferrite structure ((Cu,Fe)Fe2O4) and/or precipitation as cuprite (Cu2O) and zero-valent copper, option 2.) copper incorporation into the ferrite structure and/or precipitation as cuprite and/or tenorite (CuO) and option 3.) copper precipitation as tenorite. Ferrite is formed by the oxidation of GR in alkaline solution without additional oxygen supply. The chemistry reaches from pure magnetite up to 45% copper ferrite component. First experiments with wastewater from electroplating industry confirm the results obtained from synthetic solutions. In all cases the volume of the precipitates is extremely low compared to typical wastewater treatment by hydroxide precipitation. Therefore, pollution and further dissipation of copper can be avoided using this simple and economic process. PMID:27290656

  12. Field test on the treatment of source zone chloroethenes using emulsified zerovalent iron

    EPA Science Inventory

    This talk summarizes the research activities currently underway at the Solid Waste Management Unit 45 (Site 45), Marine Corps Recruit Depot, Parris Island, South Carolina. A pilot field test was initiated in 2005 at this site to evaluate the effectiveness of nanoscale emulsified...

  13. Laboratory comparison of four iron-based filter materials for water treatment of trace element contaminants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A laboratory investigation was conducted to evaluate four iron-based filter materials for trace element contaminant water treatment. The iron-based filter materials evaluated were zero valent iron (ZVI), porous iron composite (PIC), sulfur modified iron (SMI), and iron oxide/hydroxide (IOH). Only fi...

  14. Remediating ground water with zero-valent metals: Chemical considerations in barrier design

    SciTech Connect

    Tratnyek, P.G.; Johnson, T.L.; Scherer, M.M.; Eykholt, G.R.

    1997-12-31

    To gain perspective and insight into the performance of permeable reactive barriers containing granular iron metal, it is useful to compare the degradation kinetics of individual chlorinated solvents over a range of operating conditions. Pseudo first-order disappearance rate constants normalized to iron surface area concentration (k{sub SA}) recently have been reported for this purpose. This paper presents the results of further exploratory data analysis showing the extent to which variation in k{sub SA} is due to initial halocarbon concentration, iron type, and other factors. To aid in preliminary design calculations, representative values of k{sub SA} and a reactive transport model have been used to calculate the minimum barrier width needed for different ground water flow velocities and degrees of halocarbon conversion. Complete dechlorination of all degradation intermediates requires a wider treatment zone, but the effect is not simply additive because degradation occurs by sequential and parallel reaction pathways.

  15. Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron

    NASA Technical Reports Server (NTRS)

    Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T.

    2002-01-01

    Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation.

  16. Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron.

    PubMed

    Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T

    2002-12-15

    Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation. PMID:12521177

  17. CARBON AND SULFUR ACCUMULATION AND IRON MINERAL TRANSFORMATION IN PERMEABLE REACTIVE BARRIERS CONTAINING ZERO-VALENT IRON

    EPA Science Inventory

    Permeable reactive barrier technology is an in-situ approach for remediating groundwater contamination that combines subsurface fluid flow management with passive chemical treatment. Factors such as the buildup of mineral precipitates, buildup of microbial biomass (bio-fouling...

  18. Laboratory evaluation of zero valent iron and sulfur modified iron filter materials for agricultural drainage water treatment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    On site filter treatment systems have the potential to remove nutrients and pesticides from agricultural subsurface drainage waters. The effectiveness and efficiency of this type of drainage water treatment will depend on the actual filter materials utilized. Two promising filter materials that coul...

  19. Fundamental studies of the removal of contaminants from ground and waste waters via reduction by zero-valent metals. Annual progress report, September 1, 1996--August 31, 1997

    SciTech Connect

    Yarmoff, J.A.; Amrhein, C.

    1997-01-01

    'Contaminated groundwater is a problem throughout the US and the world. In many instances the tvpes of contamination can be directly attributed to man''s actions. For instance, the burial of wastes, casual disposal of solvents in unlined pits, and the development of irrigated agriculture have all contributed to groundwater contamination. The kinds of contaminants include chlorinated solvents and toxic trace elements that are soluble and mobile in soils and aquifers. Oxyanions of selenium. chromium. uranium. arsenic. and chlorine (as perchlorate) are frequently found as contaminants on many DOE sites. In addition. the careless disposal of cleaning solvents. such as carbon tetrachloride and trichloroethylene. has further contaminated many groundwaters at these sites. In agricultural areas of the western US, shallow groundwaters have become contaminated with high levels of selenate, chromate, and uranyl. The management of these waters requires treatment to remove the contaminants before reuse or surface water disposal. In one instance in the Central Valley of California. the discharge of selenate-contaminated shallow groundwater to a wildlife refuge caused catastrophic bird deaths and deformities of embryos. At sites where solid-propellant rocket motors were tested or disposed of, high concentrations of perchlorate and trichloroethylene are being found in the groundwater. A potential remediation method for many of these oxyanions and chlorinated-solvents is to react the contaminated water with zero-valent iron. In this reaction, the iron serves as both an electron source and as a catalyst. Elemental iron is already being used, on an experimental basis, for the reductive dechlorination of solvents and the removal of toxic trace elements. Both in situ reactive barriers and above-ground reactors are being developed for this purpose. However, the design and operation of these treatment systems requires a detailed process-level understanding of the interactions between the

  20. Reaction mechanisms involved in reduction of halogenated hydrocarbons using sulfated iron

    SciTech Connect

    Hassan, S.M.; Cipollone, M.G.; Wolfe, N.L.

    1995-12-01

    Experiments were carried out to investigate the mechanisms and pathways involved in the reduction of halogenated hydrocarbons represented by trichloroethylene (TCE) and tetrachloroethylene (PCE) with sulfated iron aqueous media. Results suggested that iron sulfide acted as the dehalogenation center. Zero-valent iron acted as a generator for molecular hydrogen through its reaction with water. Results of experiments in which iron sulfide was replaced by other transition metal sulfides and experiments in which zero-valent iron was replaced by other sources of molecular hydrogen will be reported. The main reduction product of chloroethylene derivatives was ethyne which under the catalytic reaction of zero-valent iron was reduced further to ethene and finally to ethane. Intermediate products were identified using GC-MS. Mechanisms and pathways will be presented.

  1. MS title: Catalytic oxidation and removal of arsenite in the presence of Fe ions and zero-valent Al metals.

    PubMed

    Hsu, Liang-Ching; Chen, Kai-Yue; Chan, Ya-Ting; Deng, Youjun; Hwang, Che-En; Liu, Yu-Ting; Wang, Shan-Li; Kuan, Wen-Hui; Tzou, Yu-Min

    2016-11-01

    Arsenic immobilization in acid mine drainage (AMD) is required prior to its discharge to safeguard aquatic organisms. Zero-valent aluminum (ZVAl) such as aluminum beverage cans (AlBC) was used to induce the oxidation of As(III) to As(V) and enhance the subsequent As removal from an artificially prepared AMD. While indiscernible As(III) oxidation was found in aerated ZVAl systems, the addition of 0.10-0.55mM Fe(II) or Fe(III) into the AMD significantly promoted the As(V) production. Reactions between Fe(II) and H2O2, which was produced through an oxidative reaction of ZVAl with dissolved oxygen, generated OH radicals. Such OH radicals subsequently induced the As(III) oxidation. Over the course of the Fenton like reaction, ZVAl not only directly generated the H2O2, but indirectly enhanced the OH radical production by replenishing Fe(II). Arsenite oxidation in the aerated ZVAl/Fe and AlBC/Fe systems followed zero- and first-order kinetics. Differences in the kinetic reactions of ZVAl and AlBC with respect to As(III) oxidation were attributed to higher productive efficiency of the oxidant in the AlBC systems. After the completion of As(III) oxidation, As(V) could be removed simultaneously with Al(III) and Fe(III) by increasing solution's pH to 6 to produce Al/Fe hydroxides as As(V) scavengers or to form Al/Fe/As co-precipitates. PMID:27285595

  2. Efficacy of zero-valent copper (Cu(0)) nanoparticles and reducing agents for dechlorination of mono chloroaromatics.

    PubMed

    Raut, Sandesh S; Kamble, Sanjay P; Kulkarni, Prashant S

    2016-09-01

    The zero-valent copper (Cu(0)) nanoparticles were prepared by chemical reduction method. The morphology of nanoparticles was investigated by using X ray diffraction, scanning electron microscopy-energy dispersive X ray, UV-visible spectrophotometer and Brunauer-Emmett-Teller surface area analyser. The Cu(0) nanoparticles along with reducing agents, NaBH4/5% acidified alcohol were used for the dechlorination of chloroaromatics at room temperature. Chlorobenzene (Cl-B), chlorotoluene (Cl-T), chloropyridine (Cl-Py) and chlorobiphenyl (Cl-BPh) were selected as the contaminants. The effect of various operating parameters such as pH, concentration of the catalyst and reducing agent (NaBH4), and recycling of the catalyst on dechlorination were studied. Nearly complete dechlorination of all the chloroaromatics were achieved in the presence of Cu(0) nanoparticles (2.5 g L(-1)) and NaBH4 (1.0 g L(-1)) within 12 h. On the contrary, approximately 70% of dechlorination was observed in the presence of 5% acidified alcohol at similar experimental conditions. The dechlorination mechanism highlighted the importance of Cu(0) nanoparticles as a surface mediator. The kinetics of the dechlorination of chloroaromatics was investigated and compared with chloroaliphatics. The dechlorination rate differed from 0.23 h(-1) (Cl-B) to 0.15 h(-1) (Cl-BPh) in the presence of Cu(0) nanoparticles and NaBH4. The effectiveness of Cu(0) nanoparticles with NaBH4 (1 g L(-1)) and 5% acidified alcohol as electron donors were studied by oxidation-reduction potential and observed to be -1016 mV and -670 mV, respectively. Final products of the dechlorination were benzene, toluene, pyridine and biphenyl, as identified by gas chromatograph mass spectrometer and nuclear magnetic resonance spectroscopy. PMID:27318451

  3. Reduction of Chromium(VI) mediated by zero-valent magnesium under neutral pH conditions.

    PubMed

    Lee, Giehyeon; Park, Jaeseon; Harvey, Omar R

    2013-03-01

    In an effort to assess the potential use of ZVMg in contaminant treatments, we examined Cr(VI) reduction mediated by ZVMg particles under neutral pH conditions. The reduction of Cr(VI) was tested with batch experiments by varying [Cr(VI)](0) (4.9, 9.6, 49.9 or 96.9 μM) in the presence of 50 mg/L ZVMg particles ([Mg(0)](0) = 2.06 mM) at pH 7 buffered with 50 mM Na-MOPS. When [Cr(VI)](0) = 4.9 or 9.6 μM, Cr(VI) was completely reduced within 60 min. At higher [Cr(VI)](0) (49.9 or 96.9 μM), by contrast, the reduction became retarded at >120 min likely due to rapid ZVMg dissolution in water and surface precipitation of Cr(III) on ZVMg particles. Surface precipitation was observed only when [Cr(VI)](0) = 49.9 or 96.9 μM and increased with increasing [Cr(VI)](0). The effect of dissolved oxygen was negligible on the rate and extent of Cr(VI) reduction. Experimental results indicated that Cr(VI) was reduced not directly by ZVMg but by reactive intermediates produced from ZVMg-water reaction under the experimental conditions employed in this study. In addition, the observed rates of Cr(VI) reduction appeared to follow an order below unity (0.19) with respect to [Cr(VI)](0). These results imply that ZVMg-mediated Cr(VI) reduction likely occurred via an alternative mechanism to the direct surface-mediated reduction typically observed for other zero-valent metals. Rapid and complete Cr(VI) reduction was achieved when a mass ratio of [ZVMg](0):[Cr(VI)](0) ≥ 100 at neutral pH under both oxic and anoxic conditions. Our results highlights the potential for ZVMg to be used in Cr(VI) treatments especially under neutral pH conditions in the presence of dissolved oxygen. PMID:23253471

  4. Removal of high concentration p-nitrophenol in aqueous solution by zero valent iron with ultrasonic irradiation (US-ZVI).

    PubMed

    Lai, Bo; Chen, Zhaoyu; Zhou, Yuexi; Yang, Ping; Wang, Juling; Chen, Zhiqiang

    2013-04-15

    In this study, the US-ZVI system was used to produce the strong reductants including H and nascent Fe(2+) ions to eliminate the toxicity of the high concentration p-nitrophenol (PNP) wastewater. The effect of the reactor structure, initial pH, ZVI dosage, ultrasonic power and initial PNP concentration on the removal efficiency of PNP from water was investigated intensively. The results show that a higher removal rate can be obtained by using a conical structure reactor, and the lower initial pH can aid the acceleration of PNP removal rate by using US-ZVI system. Furthermore, the removal efficiencies of PNP increased obviously with the increase of initial ZVI concentration from 0 to 15 gL(-1). Also, the treatment capacity of ZVI was enhanced remarkably by the ultrasonic irradiation, and the US-ZVI system can maintain high treatment efficiency for the high concentration PNP wastewater (500-10,000 mgL(-1)). Meanwhile, the high removal efficiency of PNP was mainly resulted from the synergistic reaction of ZVI and US. At last, the main degradation product (i.e., p-aminophenol) was detected by gas chromatography-mass spectrum (GC-MS). Thus, the reaction pathway of PNP in the US-ZVI system is proposed as a reducing process by the H and nascent Fe(2+) ions. PMID:23454461

  5. Experimental Determination of the Dissolution Kinetics of Zero-Valent Iron in the Presence of Organic Complexants

    SciTech Connect

    Pierce, Eric M.; Wellman, Dawn M.; Lodge, Alex M.; Rodriguez, Elsa A.

    2007-08-17

    Single-pass flow-through tests were conducted under conditions of relatively constant dissolved O2 [O2 (aq)] over the pH(23°C) range (from 7 to 12) and temperature (23° to 90°C) in the presence of EDTA and EDDHA to maintain dilute conditions and minimize the formation of a partially oxidized surface film and Fe-bearing secondary phase(s) during testing. These results indicate that the corrosion of Fe(0) is relatively insensitive to pH and temperature and the forward rate is 3 to 4 orders of magnitude higher than when a passive film and corrosion products are present. Tests conducted with Amasteel (a low carbon steel) and 99Tc-bearing Fe(0) metal indicated that the forward dissolution rates for both metals were similar, if not identical. In other words, under these test conditions the presence of P and 99Tc in the 99Tc-bearing Fe(0) metal appeared to have little effect on the forward dissolution rate and subsequent release of 99Tc.

  6. A MD Simulation and Analysis for Aggregation Behaviors of Nanoscale Zero-Valent Iron Particles in Water via MS

    PubMed Central

    Liu, Dongmei; Tang, Huan; Lu, Jing; Cui, Fuyi

    2014-01-01

    With the development of nanotechnology, more nanomaterials will enter into water environment system. Studying the existing form of nanomaterials in water environment will help people benefit from the correct use of them and to reduce the harm to human caused by them for some nanomaterials can bring polluting effect. Aggregation is a main behavior for nanoparticle in water environment. NZVI are used widely in many fields resulting in more NZVI in water environment. Molecular dynamics simulations and Materials Studio software are used to investigate the microaggregation behaviors of NZVI particles. Two scenes are involved: (1) particle size of NZVI in each simulation system is the same, but initial distance of two NZVI particles is different; (2) initial distance of two NZVI particles in each simulation system is the same, but particle size of NZVI is different. Atomistic trajectory, NP activity, total energy, and adsorption of H2O are analyzed with MS. The method provides new quantitative insight into the structure, energy, and dynamics of the aggregation behaviors of NZVI particles in water. It is necessary to understand microchange of NPs in water because it can provide theoretical research that is used to reduce polluting effect of NPs on water environment. PMID:25250388

  7. THE DIVERSITY OF CONTAMINANT REDUCTION REACTIONS BY ZERO-VALENT IRON: ROLE OF THE REDUCTATE. (R827117)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  8. Zero-valent Fe confined mesoporous silica nanocarriers (Fe(0) @ MCM-41) for targeting experimental orthotopic glioma in rats.

    PubMed

    Shevtsov, M A; Parr, M A; Ryzhov, V A; Zemtsova, E G; Arbenin, A Yu; Ponomareva, A N; Smirnov, V M; Multhoff, G

    2016-01-01

    Mesoporous silica nanoparticles (MSNs) impregnated with zero-valent Fe (Fe(0) @ MCM-41) represent an attractive nanocarrier system for drug delivery into tumor cells. The major goal of this work was to assess whether MSNs can penetrate the blood-brain barrier in a glioblastoma rat model. Synthesized MSNs nanomaterials were characterized by energy dispersive X-ray spectroscopy, measurements of X-ray diffraction, scanning electron microscopy and Mössbauer spectroscopy. For the detection of the MSNs by MR and for biodistribution studies MSNs were labeled with zero-valent Fe. Subsequent magnetometry and nonlinear-longitudinal-response-M2 (NLR-M2) measurements confirmed the MR negative contrast enhancement properties of the nanoparticles. After incubation of different tumor (C6 glioma, U87 glioma, K562 erythroleukemia, HeLa cervix carcinoma) and normal cells such as fibroblasts and peripheral blood mononuclear cells (PBMCs) MSNs rapidly get internalized into the cytosol. Intracellular residing MSNs result in an enhanced cytotoxicity as Fe(0) @ MCM-41 promote the reactive oxygen species production. MRI and histological studies indicated an accumulation of intravenously injected Fe(0) @ MCM-41 MSNs in orthotopic C6 glioma model. Biodistribution studies with measurements of second harmonic of magnetization demonstrated an increased and dose-dependent retention of MSNs in tumor tissues. Taken together, this study demonstrates that MSNs can enter the blood-brain barrier and accumulate in tumorous tissues. PMID:27386761

  9. Zero-valent Fe confined mesoporous silica nanocarriers (Fe(0) @ MCM-41) for targeting experimental orthotopic glioma in rats

    PubMed Central

    Shevtsov, M. A.; Parr, M. A.; Ryzhov, V. A.; Zemtsova, E. G.; Arbenin, A. Yu; Ponomareva, A. N.; Smirnov, V. M.; Multhoff, G.

    2016-01-01

    Mesoporous silica nanoparticles (MSNs) impregnated with zero-valent Fe (Fe(0) @ MCM-41) represent an attractive nanocarrier system for drug delivery into tumor cells. The major goal of this work was to assess whether MSNs can penetrate the blood-brain barrier in a glioblastoma rat model. Synthesized MSNs nanomaterials were characterized by energy dispersive X-ray spectroscopy, measurements of X-ray diffraction, scanning electron microscopy and Mössbauer spectroscopy. For the detection of the MSNs by MR and for biodistribution studies MSNs were labeled with zero-valent Fe. Subsequent magnetometry and nonlinear-longitudinal-response-M2 (NLR-M2) measurements confirmed the MR negative contrast enhancement properties of the nanoparticles. After incubation of different tumor (C6 glioma, U87 glioma, K562 erythroleukemia, HeLa cervix carcinoma) and normal cells such as fibroblasts and peripheral blood mononuclear cells (PBMCs) MSNs rapidly get internalized into the cytosol. Intracellular residing MSNs result in an enhanced cytotoxicity as Fe(0) @ MCM-41 promote the reactive oxygen species production. MRI and histological studies indicated an accumulation of intravenously injected Fe(0) @ MCM-41 MSNs in orthotopic C6 glioma model. Biodistribution studies with measurements of second harmonic of magnetization demonstrated an increased and dose-dependent retention of MSNs in tumor tissues. Taken together, this study demonstrates that MSNs can enter the blood-brain barrier and accumulate in tumorous tissues. PMID:27386761

  10. Iron Nanoparticles in Reactive Environmental Barriers

    SciTech Connect

    Nuxoll, Eric E.; Shimotori, Tsutomu; Arnold, William A.; Cussler, Edward L.

    2003-09-23

    Zero-valent iron is cheap, environmentally innocuous, and effective at reducing chlorinated organics. It has, as a result, become a popular candidate for remediating aquifers contaminated with trichloroethylene and other halogenated pollutants. In this paper, we discuss one such system, where iron nanoparticles are synthesized and incorporated into polyvinyl alcohol membranes, forming water-permeable barriers to these pollutants. These barriers are tested against a variety of contaminants, including carbon tetrachloride, copper, and chromate.

  11. FUNDAMENTAL STUDIES OF THE REMOVAL OF CONTAMINANTS FROM GROUND AND WASTE WATERS VIA REDUCTION BY ZERO-VALENT METALS

    EPA Science Inventory

    In an effort to remove trace contaminants from wastewaters and groundwaters, elemental iron is being used for the reductive dechlorination of solvents and the removal of toxic trace elements, such as Se, Cr, and U. Both in situ reactive barriers and above-ground reactors are bein...

  12. Use of Electrophoresis for Transporting Nano-Iron in Porous Media

    EPA Science Inventory

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

  13. REMOVAL OF TNT AND RDX FROM WATER AND SOIL USING IRON METAL. (R825549C043)

    EPA Science Inventory

    Contaminated water and soil at active or abandoned munitions plants is a serious problem since these compounds pose risks to human health and can be toxic to aquatic and terrestrial life. Our objective was to determine if zero-valent iron (Fe0) could be used to p...

  14. 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...

  15. IN SITU REMEDIATION OF CONTAMINANTS IN GROUND WATER & SOILS USING PERMEABLE REACTIVE BARRIERS (PHASE I, CHROMIUM, CHLORINATED ORGANICS & ZERO-VALENT IRON) RSRP3

    EPA Science Inventory

    The primary objective of this research is to select an effective reductant for detoxification and immobilization of hexavalent chromium present in the soils/sediments collected from the old plating shop of the U.S. Coast Guard Air Support Center, Elizabeth City, North Carolina. ...

  16. EFFECTS OF CARBONATE SPECIES ON THE KINETICS OF DECHLORINATION OF 1,1,1-TRICHLOROETHANE BY ZERO-VALENT IRON. (R827117)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  17. INFLUENCE OF GROUNDWATER GEOCHEMISTRY ON THE LONG-TERM PERFORMANCE OF IN-SITU PERMEABLE REACTIVE BARRIERS CONTAINING ZERO-VALENT IRON

    EPA Science Inventory

    Reactive barriers that couple subsurface fluid flow with a passive chemical treatment zone are emerging, cost effective approaches for in-situ remediation of contaminated groundwater. Factors such as the build-up of surface precipitates, bio-fouling, and changes in subsurface tr...

  18. Reduction of Contaminant Mobility at the TNX Outfall Delta Through the Use of Apatite and Zero-Valent Iron as Soil Amendments

    SciTech Connect

    Kaplan, D.

    2002-12-18

    The TNX pilot-scale research facility released processed waste, containing high concentrations of several metals and radionuclides into an unlined seepage basin between 1958 and 1980. The contents of this basin have entered the nearby swamp, the TNX Outfall Delta (TNX OD), by subsurface and overland flow. A multi-faceted strategy has been proposed recently for mitigating contaminant migration at the site. The intent of this remediation strategy is not only to minimize contaminant leaching in a cost-effective manner, but also to minimize harm to the sensitive TNX wetland ecosystem.

  19. Treatment of mature landfill leachate by internal micro-electrolysis integrated with coagulation: a comparative study on a novel sequencing batch reactor based on zero valent iron.

    PubMed

    Ying, Diwen; Peng, Juan; Xu, Xinyan; Li, Kan; Wang, Yalin; Jia, Jinping

    2012-08-30

    A comparative study of treating mature landfill leachate with various treatment processes was conducted to investigate whether the method of combined processes of internal micro-electrolysis (IME) without aeration and IME with full aeration in one reactor was an efficient treatment for mature landfill leachate. A specifically designed novel sequencing batch internal micro-electrolysis reactor (SIME) with the latest automation technology was employed in the experiment. Experimental data showed that combined processes obtained a high COD removal efficiency of 73.7 ± 1.3%, which was 15.2% and 24.8% higher than that of the IME with and without aeration, respectively. The SIME reactor also exhibited a COD removal efficiency of 86.1 ± 3.8% to mature landfill leachate in the continuous operation, which is much higher (p<0.05) than that of conventional treatments of electrolysis (22.8-47.0%), coagulation-sedimentation (18.5-22.2%), and the Fenton process (19.9-40.2%), respectively. The innovative concept behind this excellent performance is a combination effect of reductive and oxidative processes of the IME, and the integration electro-coagulation. Optimal operating parameters, including the initial pH, Fe/C mass ratio, air flow rate, and addition of H(2)O(2), were optimized. All results show that the SIME reactor is a promising and efficient technology in treating mature landfill leachate. PMID:22771343

  20. Comparative study on the reactivity of Fe/Cu bimetallic particles and zero valent iron (ZVI) under different conditions of N2, air or without aeration.

    PubMed

    Xiong, Zhaokun; Lai, Bo; Yang, Ping; Zhou, Yuexi; Wang, Juling; Fang, Shuping

    2015-10-30

    In order to further compare the degradation capacity of Fe(0) and Fe/Cu bimetallic system under different aeration conditions, the mineralization of PNP under different aeration conditions has been investigated thoroughly. The results show that the removal of PNP by Fe(0) or Fe/Cu system followed the pseudo-first-order reaction kinetics. Under the optimal conditions, the COD removal efficiencies obtained through Fe(0) or Fe/Cu system under different aeration conditions followed the trend that Fe/Cu (air)>Fe/Cu (N2: 0-30 min, air: 30-120 min)>control-Fe (air)>Fe/Cu (without aeration)>Fe/Cu (N2)>control-Fe (N2). It revealed that dissolved oxygen (DO) could improve the mineralization of PNP, and Cu could enhance the reactivity of Fe(0). In addition, the degradation of PNP was further analyzed by using UV-vis, FTIR and GC/MS, and the results suggest that Fe/Cu bimetallic system with air aeration could completely break the benzene ring and NO2 structure of PNP and could generate the nontoxic and biodegradable intermediate products. Meanwhile, most of these intermediate products were further mineralized into CO2 and H2O, which brought about a high COD removal efficiency (83.8%). Therefore, Fe/Cu bimetallic system with air aeration would be a promising process for toxic refractory industry wastewater. PMID:25978189

  1. Effect of pH on the dissolution kinetics of zero-valent iron in the presence of EDDHA and EDTA

    SciTech Connect

    Lodge, Alexander M.; Pierce, Eric M.; Wellman, Dawn M.; Cordova, Elsa A.

    2007-03-25

    The effect of environmental factors (e.g., pH, solution composition, and temperature) that affect the longevity of Fe(0) barriers in the subsurface are difficult to quantify independently from changes that occur to the passivating layer. Therefore, to quantify the rate of Fe(0) dissolution under conditions which maintain the pO2 at a relatively constant level and minimize the formation of a passivating layer on the metal surface, a series of experiments have been conducted with the single-pass flow-through (SPFT) apparatus. These experiments were conducted over the pH range from 7.0 to 12.0 at 90°C in the presence of 5 mM EDDHA or 5 mM EDTA. The organic acids, EDDHA and EDTA, helped to maintain the aqueous Fe concentration below saturation with respect to Fe-bearing alteration phases and minimize the formation of a partially oxidized surface film. Results suggest the corrosion of Fe(0) is relatively insensitive to pH and the forward or maximum dissolution rate is 3 to 4 orders of magnitude higher than when a passive film and corrosion products are present.

  2. Iron enhanced abiotic degradation of chlorinated hydrocarbons

    SciTech Connect

    Chen, C.T.

    1995-10-01

    Since the 1970s, several researchers have investigated the ability of certain zero-valent metals or alloys to enhance the degradation of halogenated organic compounds in contaminated water. Iron, zinc, aluminum, brass, copper, and stainless steel have been studied at various times with varying degrees of success. Gillham and O`Hannesin have recently made a literature review and conducted tests on 14 halogenated aliphatic compounds using zero-valent iron as an enhancing agent. The results showed that rapid dehalogenation occurred on all of the compounds tested except dichloromethane. Based on these test results, EnviroMetal Technologies, Inc. proposed to remediate groundwater contaminated with chlorinated organic compounds using this technology. The EPA Superfund Innovative Technology Evaluation (SITE) program has accepted this technology for demonstration. This demonstration project will include two processes, above ground reactor and in situ permeable wall. The demonstration on the above ground reactor is being conducted at a site in Wayne, New Jersey. The main contaminants at this site are tetrachloroethene (PCE) and trichloroethene (TCE). The in situ permeable wall process will be conducted at a site in upstate New York. This site is a shallow sand aquifer containing TCE, dichloroethenes, and 1,1,1-trichloroethane.

  3. EZVI Injection Field Test Leads to Pilot-Scale Application

    EPA Science Inventory

    Testing and monitoring of emulsified zero-valent ironTM (EZVI) injections was conducted at Cape Canaveral Air Force Station’s Launch Complex 34, FL, in 2002 to 2005 to evaluate the technology’s efficacy in enhancing in situ dehalogenation of dense nonaqueous-phase liquid (DNAPL) ...

  4. THE EFFECT OF SMECTITE ON THE CORROSION OF IRON METAL

    SciTech Connect

    Balko, Barbara A.; Bosse, Stephanie A.; Cade, Anne E.; Jones-Landry, Elise F.; Amonette, James E.; Daschbach, John L.

    2012-04-24

    The combination of zero-valent iron and a clay-type amendment is often observed to have a synergistic effect on the rate of reduction reactions. In this paper, electrochemical techniques are used to determine the mechanism of interaction between the iron and smectite clay minerals. Iron electrodes coated with an evaporated smectite suspension (clay-modified iron electrodes, CMIEs) were prepared using five different smectites: SAz-1, SWa-1, STx-1, SWy-1, and SHCa-1. All the smectites were exchanged with Na+ and one sample of SWy-1 was also exchanged with Mg2+. Potentiodynamic potential scans and cyclic voltammograms were taken using the CMIEs and uncoated but passivated iron electrodes. These electrochemical experiments, along with measurements of the amount of Fe2+ and Fe3+ sorbed in the smectite coating, suggested that the smectite removed the passive layer of the underlying iron electrode during the evaporation process. Cyclic voltammograms taken after the CMIEs were biased at the active-passive transition potential for varying amounts of time suggested that the smectite limited growth of a passive layer, preventing passivation. These results are attributed to the Broensted acidity of the smectite as well as to its ability to sorb iron cations. Oxides that did form on the surface of the iron in the presence of the smectite when it was biased anodically seemed to be different than those that form on the surface of an uncoated iron electrode under otherwise similar conditions; this difference suggested that the smectite reacted with the Fe2+ formed from the oxidation of the underlying iron. No significant correlation could be found between the ability of the smectite to remove the iron passive film and the smectite type. The results have implications for the mixing of sediments and iron particles in permeable reactive barriers, underground storage of radioactive waste in steel canisters, and the use of smectite supports in preventing aggregation of nano-sized zero-valent

  5. Carbon isotope fractionation during reductive dechlorination of TCE in batch experiments with iron samples from reactive barriers.

    PubMed

    Schüth, Christoph; Bill, Markus; Barth, Johannes A C; Slater, Gregory F; Kalin, Robert M

    2003-10-01

    Reductive dechlorination of trichloroethene (TCE) by zero-valent iron produces a systematic enrichment of 13C in the remaining substrate that can be described using a Rayleigh model. In this study, fractionation factors for TCE dechlorination with iron samples from two permeable reactive barriers (PRBs) were established in batch experiments. Samples included original unused iron as well as material from a barrier in Belfast after almost 4 years of operation. Despite the variety of samples, carbon isotope fractionations of TCE were remarkably similar and seemed to be independent of iron origin, reaction rate, and formation of precipitates on the iron surfaces. The average enrichment factor for all experiments was -10.1 per thousand (+/- 0.4 per thousand). These results indicate that the enrichment factor provides a powerful tool to monitor the reaction progress, and thus the performance, of an iron-reactive barrier over time. The strong fractionation observed may also serve as a tool to distinguish between insufficient residence time in the wall and a possible bypassing of the wall by the plume, which should result in an unchanged isotopic signature of the TCE. Although further work is necessary to apply this stable isotope method in the field, it has potential to serve as a unique monitoring tool for PRBs based on zero-valent iron. PMID:14516939

  6. Reduction of selenite on iron surfaces: Amicro-spectroscopic study

    NASA Astrophysics Data System (ADS)

    Scheidegger, A. M.; Grolimund, D.; Cui, D.; Devoy, J.; Spahiu, K.; Wersin, P.; Bonhoure, I.; Janousch, M.

    2003-03-01

    Under anoxie conditions zero-valent iron can react with water to produce hydrogen gas and magnetite or green rust, a highly reactive mineral phase that can induce reduction processes and thus control the speciation, the solubility, toxicity and the mobility of redox sensitive elements in (nuclear) waste repositories. In this study micro X-ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS) were used to investigate the speciation of selenium that immobilized in the presence of Fe(0) and an anoxie synthetic groundwater solution. The selenium immobilization was accompanied by the formation of a green rust corrosion layer. Micro-XRF revealed that a Se-rich layer is present along the iron surfaces that were exposed to the Se(IV) solution. Micro-XAS experiments at the Se K-edge showed that Se(IV) was reduced to elemental Se(0). Thus, the reactivity of zero-valent and green rust should to be considered in assessing the long-term fate of selenium in nuclear waste repositories.

  7. RCRA corrective measures using a permeable reactive iron wall US Coast Guard Support Center, Elizabeth City, North Carolina

    SciTech Connect

    Schmithors, W.L.; Vardy, J.A.

    1997-12-31

    A chromic acid release was discovered at a former electroplating shop at the U.S. Coast Guard Support Center in Elizabeth City, North Carolina. Initial investigative activities indicated that chromic acid had migrated into the subsurface soils and groundwater. In addition, trichloroethylene (TCE) was also discovered in groundwater during subsequent investigations of the hexavalent chromium (Cr VI) plume. Corrective measures were required under the Resource Conservation and Recovery Act (RCRA). The in-situ remediation method, proposed under RCRA Interim Measures to passively treat the groundwater contaminants, uses reactive zero-valent iron to reductively dechlorinate the chlorinated compounds and to mineralize the hexavalent chromium. A 47 meter by 0.6 meter subsurface permeable iron wall was installed downgradient of the source area to a depth of 7 meters using a direct trenching machine. The iron filings were placed in the ground as the soils were excavated from the subsurface. This is the first time that direct trenching was used to install reactive zero-valent iron filings. Over 250 metric tons of iron filings were used as the reactive material in the barrier wall. Installation of the iron filings took one full day. Extensive negotiations with regulatory agencies were required to use this technology under the current facility Hazardous Waste Management Permit. All waste soils generated during the excavation activities were contained and treated on site. Once contaminant concentrations were reduced the waste soils were used as fill material.

  8. Influence of structure of iron nanoparticles in aggregates on their magnetic properties

    NASA Astrophysics Data System (ADS)

    Rosická, Dana; Šembera, Jan

    2011-09-01

    Zero-valent iron nanoparticles rapidly aggregate. One of the reasons is magnetic forces among the nanoparticles. Magnetic field around particles is caused by composition of the particles. Their core is formed from zero-valent iron, and shell is a layer of magnetite. The magnetic forces contribute to attractive forces among the nanoparticles and that leads to increasing of aggregation of the nanoparticles. This effect is undesirable for decreasing of remediation properties of iron particles and limited transport possibilities. The aggregation of iron nanoparticles was established for consequent processes: Brownian motion, sedimentation, velocity gradient of fluid around particles and electrostatic forces. In our previous work, an introduction of influence of magnetic forces among particles on the aggregation was presented. These forces have significant impact on the rate of aggregation. In this article, a numerical computation of magnetic forces between an aggregate and a nanoparticle and between two aggregates is shown. It is done for random position of nanoparticles in an aggregate and random or arranged directions of magnetic polarizations and for structured aggregates with arranged vectors of polarizations. Statistical computation by Monte Carlo is done, and range of dominant area of magnetic forces around particles is assessed.

  9. 7 CFR 58.631 - Emulsifiers.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Specifications for Dairy Plants Approved for USDA Inspection and Grading Service 1 Quality Specifications for Raw Material § 58.631 Emulsifiers. Emulsifiers shall be clean and wholesome and consist of one or more of...

  10. 7 CFR 58.631 - Emulsifiers.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Specifications for Dairy Plants Approved for USDA Inspection and Grading Service 1 Quality Specifications for Raw Material § 58.631 Emulsifiers. Emulsifiers shall be clean and wholesome and consist of one or more of...

  11. Reductive dechlorination of chlorinated alkanes and alkenes by iron metal and metal mixtures

    SciTech Connect

    Orth, R.G.; McKenzie, D.E.

    1995-12-31

    Reductive dechlorination using zero valent metals such as iron has seen an increase in interest over the past few years with the extension of iron dechlorination to in-situ treatment of ground water using a process developed by Gillham and O`Hannes in 1994. Earlier applications included the use of metals for water treatment for the degradation of halogenated pesticides. This increased interest is demonstrated by the recent ACS symposium on zero valent metal dechlorination. The work that will be presented involves the reduction of selected chlorinated alkanes and alkenes beginning with chlorobutanes. The position of the chlorines on the carbon chain relative to each other was studied by determining the rates of the dechlorination processes. These studies were carried out in seated batch reactors so that loss of the chlorinated hydrocarbons was minimized and total carbon and chloride mass balances could be obtained. The goal of the studies was to understand the mechanism of the reaction that is believed to follow metal corrosion processes involving two electron transfer reactions.

  12. Optimization of processing temperature in the nitridation process for the synthesis of iron nitride nanoparticles

    NASA Astrophysics Data System (ADS)

    Rohith Vinod, K.; Saravanan, P.; Sakar, M.; Balakumar, S.

    2015-06-01

    We have demonstrated an effective strategy on the nitridation process to synthesize ɛ-Fe3N nanoparticles (NPs) from the zero valent iron NPs as a starting material. The transformation of iron into iron nitride phase was systematically studied by performing the nitridation process at different processing temperatures. The phase, crystal structure was analyzed by XRD. Morphology and size of the ZVINPs and ɛ-Fe3N NPs were analyzed by field emission scanning electron microscope. Further, their room temperature magnetic properties were studied by using vibrating sample magnetometer and it revealed that the magnetic property of ɛ-Fe3N is associated with ratio of Fe-N in the iron nitride system.

  13. Optimization of processing temperature in the nitridation process for the synthesis of iron nitride nanoparticles

    SciTech Connect

    Rohith Vinod, K.; Sakar, M.; Balakumar, S.; Saravanan, P.

    2015-06-24

    We have demonstrated an effective strategy on the nitridation process to synthesize ε-Fe{sub 3}N nanoparticles (NPs) from the zero valent iron NPs as a starting material. The transformation of iron into iron nitride phase was systematically studied by performing the nitridation process at different processing temperatures. The phase, crystal structure was analyzed by XRD. Morphology and size of the ZVINPs and ε-Fe{sub 3}N NPs were analyzed by field emission scanning electron microscope. Further, their room temperature magnetic properties were studied by using vibrating sample magnetometer and it revealed that the magnetic property of ε-Fe{sub 3}N is associated with ratio of Fe-N in the iron nitride system.

  14. Enrichment and encapsulation of uranium with iron nanoparticle.

    PubMed

    Ling, Lan; Zhang, Wei-Xian

    2015-03-01

    The ability to recover uranium from water is significant because of its potential applications on nuclear fuel capture and mitigation of nuclear wastes. In this work, a unique nanostructure is presented by which trace level (2.32-882.68 μg/L) uranium can be quickly separated from water and encapsulated at the center of zero-valent iron nanoparticles. Over 90% of the uranium is recovered with 1 g/L nanoparticles in less than 2 min. Near atomic-resolution elemental mapping on the U(VI) intraparticle reactions in a single iron nanoparticle is obtained with aberration corrected scanning transmission electron microscopy, which provides direct evidence on U(VI) diffusion, reduction to U(IV), and deposition in the core area. PMID:25689272

  15. Iron

    MedlinePlus

    Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

  16. 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

  17. Nano-iron Tracer Test for Characterizing Preferential Flow Path in Fractured Rock

    NASA Astrophysics Data System (ADS)

    Chia, Y.; Chuang, P. Y.

    2015-12-01

    Deterministic description of the discrete features interpreted from site characterization is desirable for developing a discrete fracture network conceptual model. It is often difficult, however, to delineate preferential flow path through a network of discrete fractures in the field. A preliminary cross-borehole nano-iron tracer test was conducted to characterize the preferential flow path in fractured shale bedrock at a hydrogeological research station. Prior to the test, heat-pulse flowmeter measurements were performed to detect permeable fracture zones at both the injection well and the observation well. While a few fracture zones are found permeable, most are not really permeable. Chemical reduction method was used to synthesize nano zero-valent iron particles with a diameter of 50~150 nm. The conductivity of nano-iron solution is about 3100 μs/cm. The recorded fluid conductivity shows the arrival of nano-iron solution in the observation well 11.5 minutes after it was released from the injection well. The magnetism of zero-valent iron enables it to be absorbed on magnet array designed to locate the depth of incoming tracer. We found nearly all of absorbed iron on the magnet array in the observation well were distributed near the most permeable fracture zone. The test results revealed a preferential flow path through a permeable fracture zone between the injection well and the observation well. The estimated hydraulic conductivity of the connected fracture is 2.2 × 10-3 m/s. This preliminary study indicated that nano-iron tracer test has the potential to characterize preferential flow path in fractured rock.

  18. Implementation of fluidized granulated iron reactors in a chromate remediation process.

    PubMed

    Müller, P; Lorber, K E; Mischitz, R; Weiss, C

    2014-07-01

    A new approach concerning in-situ remediation on source ('hot-spot') decontamination of a chromate damage in connection with an innovative pump-and-treat-technique has been developed. Iron granulates show significant higher reduction rates, using fluidized bed conditions, than a literature study with a fixed bed installation of small-sized iron granules. First results from an abandoned tannery site concerning injections of sodium dithionite as a chromate reductant for the vadose zone in combination with a pump-and-treat-method, allying the advantages of granulated zero valent iron (ZVI), are reported. Reduction amounts of chromate have been found up to 88% compared with initial values in the soil after a soil water exchange of 8 pore volumes within 2.5 months. Chromate concentrations in the pumped effluent have been reduced to under the detection limit of 0.005 mg/L by treatment with ZVI in the pilot plant. PMID:24530188

  19. Dechlorination of carbon tetrachloride by iron metal: Effect of reactant concentrations

    SciTech Connect

    Scherer, M.M.; Tratnyek, P.G.

    1995-12-01

    Optimal application of zero-valent iron (Fe{sup 0}) in contaminant remediation requires an understanding of the mechanism by which the process occurs. An important first step towards developing such an understanding is determining the dependence of reaction rate on the concentration of each reactant. Previous efforts by Matheson and Tratnyek (1994) found that the first-order rate constant for reduction of CCl{sub 4} by Fe{sup 0} increased linearly with iron surface area. However, heterogeneous systems often exhibit more complex behavior, suggesting that the simple linear relationships previously reported may not fully reflect all of the potentially contributing processes. To investigate this possibility, further study of the effect of initial CCl{sub 4} concentration and iron surface area has been undertaken. Our findings suggest that site availability arguments can be applied to the effect of CCl{sub 4} concentration but that the effect of Fe{sup 0} surface area is more complex.

  20. 7 CFR 58.722 - Emulsifying agents.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... Specifications for Dairy Plants Approved for USDA Inspection and Grading Service 1 Quality Specifications for Raw Material § 58.722 Emulsifying agents. Emulsifying agents shall be those permitted by the Food and Drug Administration for the specific pasteurized process cheese product, and shall be free from extraneous...

  1. 7 CFR 58.722 - Emulsifying agents.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... Specifications for Dairy Plants Approved for USDA Inspection and Grading Service 1 Quality Specifications for Raw Material § 58.722 Emulsifying agents. Emulsifying agents shall be those permitted by the Food and Drug Administration for the specific pasteurized process cheese product, and shall be free from extraneous...

  2. IRON

    EPA Science Inventory

    The document surveys the effects of organic and inorganic iron that are relevant to humans and their environment. The biology and chemistry of iron are complex and only partially understood. Iron participates in oxidation reduction processes that not only affect its geochemical m...

  3. Laboratory Evaluation of Sulfur Modified Iron for Use as a Filter Material to Treat Agricultural Drainage Waters

    NASA Astrophysics Data System (ADS)

    Allred, B. J.

    2009-12-01

    Where subsurface drainage practices are employed, fertilizer nutrients and pesticides applied on farm fields and municipal locations are commonly intercepted by the buried drainage pipes and then discharged into local streams and lakes, oftentimes producing adverse environmental impacts on these surface water bodies. On-site water filter treatment systems can be employed to prevent the release of agricultural nutrients/pesticides into adjacent waterways. Sulfur modified iron is a relatively unknown industrial product that may have promise for use as a filter material to remove contaminants from subsurface drainage waters. Sulfur modified iron (SMI) is a high surface area iron powder (zero valent iron) that has been altered via chemical reaction with pure sulfur to produce a sulfur/iron surface coating on the iron particles. A laboratory investigation was conducted with contaminant removal batch tests, saturated falling-head hydraulic conductivity tests, and saturated solute transport column experiments to evaluate the feasibility for using SMI to treat subsurface drainage waters. Contaminant removal batch tests showed that three SMI samples were much more effective removing nitrate (> 94% nitrate removed) than three zero valent iron samples (< 10% nitrate removed). Batch test results additionally showed that SMI removed greater that 94% of dissolved phosphate, but was not particularly effective removing the pesticide, atrazine (< 37% atrazine removed). Hydraulic conductivity tests indicated that all three SMI samples that were evaluated had sufficient hydraulic conductivity, much greater than the 1 x 10-3 cm/s standard used for stormwater sand filters. The saturated solute transport tests confirmed that SMI can be effective removing nitrate and phosphate from drainage waters. Analysis of column effluent also showed that the large majority of nitrate removed by SMI was converted to ammonium. Consequently, these laboratory findings support the use of SMI in

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

    PubMed Central

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

    2011-01-01

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

  5. Effect of Cement on Emulsified Asphalt Mixtures

    NASA Astrophysics Data System (ADS)

    Oruc, Seref; Celik, Fazil; Akpinar, M. Vefa

    2007-10-01

    Emulsified asphalt mixtures have environmental, economical, and logistical advantages over hot mixtures. However, they have attracted little attention as structural layers due to their inadequate performance and susceptibility to early life damage by rainfall. The objective of this article is to provide an improved insight into how the mechanical properties of emulsion mixtures may be improved and to determine the influence of cement on emulsified asphalt mixtures. Laboratory tests on strength, temperature susceptibility, water damage, creep and permanent deformation were implemented to evaluate the mechanical properties of emulsified asphalt mixtures. The test results showed that mechanical properties of emulsified asphalt mixtures have significantly improved with Portland cement addition. This experimental study suggested that cement modified asphalt emulsion mixtures might be an alternate way of a structural layer material in pavement.

  6. Surface Reactivity of Core Shell Iron-Iron Oxide Nanoclusters towards Breakdown of Carbon Tetrachloride

    NASA Astrophysics Data System (ADS)

    Tarsem S., Maninder K.; Qiang, You; Kim, Hongseok; Amonette, James E.; Baer, Donald R.

    2012-02-01

    Zero-valent iron (ZVI) is one of the technologies for groundwater remediation to reduce contaminants by removal of mobile chlorinated hydrocarbons. Iron-Iron oxide (Fe/Fe3O4) nanoclusters (NCs) made in our laboratory using cluster deposition technique have enhanced reactivity towards targeted contaminants due to the presence of ZVI protected by a passivated oxide shell. Here, we investigate the effectiveness of the Fe/Fe3O4 NCs in reducing carbon tetrachloride (CT) under laboratory conditions. The reactivity of the NCs was investigated by conducting unbuffered aqueous batch experiments to reduce CT at room temperature. Initial results show that 80% of the degradation of CT resulted in the formation of dichloromethane (DCM) and chloroform (CF); the remainder likely followed a competing pathway to yield nonhazardous products such as CO. The production of undesirable hydrogenated products such as DCM and CF suggests that the dominant reaction pathway occurs through hydrogen (H) atom transfer via H atoms generated by corrosion of the iron. Comparative experiments with ZVI NCs prepared by other methods are underway and the results will be reported. Future work is to analyze and understand factors that control the reaction pathways between desirable and undesirable products.

  7. Effect of Food Emulsifiers on Aroma Release.

    PubMed

    Li, Jia-Jia; Dong, Man; Liu, Yan-Long; Zhang, Lu-Lu; Zhang, Yan; Yang, Zi-Yu; Ren, Jing-Nan; Pan, Si-Yi; Fan, Gang

    2016-01-01

    This study aimed to determine the influence of different emulsifiers or xanthan-emulsifier systems on the release of aroma compounds. Solid-phase microextraction (SPME) and GC-MS were used to study the effects of varying concentrations of xanthan gum, sucrose fatty acid ester, Tween 80 and soybean lecithin on the release of seven aroma compounds. The effects of the emulsifier systems supplemented with xanthan gum on aroma release were also studied in the same way. The results showed varying degrees of influence of sucrose fatty acid ester, soybean lecithin, Tween 80 and xanthan gum on the release of aroma compounds. Compared with other aroma compounds, ethyl acetate was more likely to be conserved in the solution system, while the amount of limonene released was the highest among these seven aroma compounds. In conclusion, different emulsifiers and complexes showed different surface properties that tend to interact with different aroma molecules. The present studies showed that the composition and structure of emulsifiers and specific interactions between emulsifiers and aroma molecules have significant effects on aroma release. PMID:27110762

  8. Iron

    MedlinePlus

    ... organ failure, coma, convulsions, and death. Child-proof packaging and warning labels on iron supplements have greatly ... levodopa that the body absorbs, making it less effective. Levodopa, found in Sinemet® and Stalevo®, is used ...

  9. Electroremediation of PCB contaminated soil combined with iron nanoparticles: Effect of the soil type.

    PubMed

    Gomes, Helena I; Dias-Ferreira, Celia; Ottosen, Lisbeth M; Ribeiro, Alexandra B

    2015-07-01

    Polychlorinated biphenyls (PCB) are carcinogenic and persistent organic pollutants that accumulate in soils and sediments. Currently, there is no cost-effective and sustainable remediation technology for these contaminants. In this work, a new combination of electrodialytic remediation and zero valent iron particles in a two-compartment cell is tested and compared to a more conventional combination of electrokinetic remediation and nZVI in a three-compartment cell. In the new two-compartment cell, the soil is suspended and stirred simultaneously with the addition of zero valent iron nanoparticles. Remediation experiments are made with two different historically PCB contaminated soils, which differ in both soil composition and contamination source. Soil 1 is a mix of soils with spills of transformer oils, while Soil 2 is a superficial soil from a decommissioned school where PCB were used as windows sealants. Saponin, a natural surfactant, was also tested to increase the PCB desorption from soils and enhance dechlorination. Remediation of Soil 1 (with highest pH, carbonate content, organic matter and PCB concentrations) obtained the maximum 83% and 60% PCB removal with the two-compartment and the three-compartment cell, respectively. The highest removal with Soil 2 were 58% and 45%, in the two-compartment and the three-compartment cell, respectively, in the experiments without direct current. The pH of the soil suspension in the two-compartment treatment appears to be a determining factor for the PCB dechlorination, and this cell allowed a uniform distribution of the nanoparticles in the soil, while there was iron accumulation in the injection reservoir in the three-compartment cell. PMID:25841071

  10. Enhancing the lipid productivity of yeasts with trace concentrations of iron nanoparticles.

    PubMed

    Pádrová, Karolína; Čejková, Alena; Cajthaml, Tomáš; Kolouchová, Irena; Vítová, Milada; Sigler, Karel; Řezanka, Tomáš

    2016-07-01

    Oxidative stress induced by zero-valent iron nanoparticles (nZVIs) was used to improve lipid accumulation in various oleaginous and non-oleginous yeasts-Candida sp., Kluyveromyces polysporus, Rhodotorula glutinis, Saccharomyces cerevisiae, Torulospora delbrueckii, Trichosporon cutaneum, and Yarrowia lipolytica. The highest lipid yields occurred at 9-13 mg/L nZVIs. Gas chromatography-mass spectrometry was used for the quantitative and qualitative analysis of the fatty acids. It showed an increasing abundance of polyunsaturated fatty acids, especially essential linoleic acid, in the presence of nZVIs. Our results suggest that nZVIs can be used to improve not only lipid production by oleaginous microorganisms but also the nutritional value of biosynthesized unsaturated fatty acids. PMID:26683688

  11. Use of electrophoresis for transporting nano-iron in porous media.

    PubMed

    Jones, Edward H; Reynolds, David A; Wood, A Lynn; Thomas, David G

    2011-01-01

    Research has been conducted to evaluate if electrophoresis could transport surface stabilized nanoscale zero-valent iron (nZVI) through fine grained sand with the intent of remediating a contaminant in situ. The experimental procedure involved determining the transport rates of polymer modified nZVI and hematite in fine grained sands under an applied electrical gradient under different physical and chemical conditions. Results indicated transport of polymer modified nZVI and hematite can be accomplished by electrophoresis, with rates found to be much higher than diffusion alone and comparable to those predicted by electrokinetic theory. This study indicates there is potential for this method to deliver polymer modified nZVI into contaminated zones within fine grained sands for the purpose of remediation. PMID:21449091

  12. The removal of nitrate by nanoscale iron particles produced using the sodium borohydride method.

    PubMed

    Cho, Hyoung-Chan; Park, Sung Hoon; Ahn, Ho-Geun; Chung, Minchul; Kim, Byungwhan; Kim, Sun-Jae; Seo, Seong-Gyu; Jung, Sang-Chul

    2011-02-01

    This study was conducted to investigate removal of nitrate by nanoscale zero-valent iron (ZVI) particles in aqueous solution. ZVI particles was produced from wasted acid that is by-products of a pickling line at a steel work. The reaction activity of ZVI particles was evaluated through decomposition experiments of NO3-N aqueous solution. Addition of a larger amount of ZVI particles resulted in a higher decomposition rate. ZVI particles showed higher decomposition efficiencies than commercially purchased ZVI particles at all pH values. Both ZVIs showed a higher decomposition rate at a lower pH. Virtually no decomposition reaction was observed at pH of 4 or higher for purchased ZVI. The ZVI particles produced directly from wasted acid by the sodium borohydride method were not easy to handle because they were very small (10-200 nm) and were oxidized easily in the air. PMID:21456267

  13. Valiant 'Zero-Valent' Effort Restores Contaminated Grounds

    NASA Technical Reports Server (NTRS)

    2005-01-01

    Dense non-aqueous phase liquids (DNAPLs) are chemical compounds that can contaminate soil and groundwater to the point of irreparability. These substances are only slightly soluble in water, and are much denser than water. Because of their solubility, DNAPLs form separate liquid phases in groundwater, and because of their density, DNAPLs sink in aquifers instead of floating at the water table, making it extremely difficult to detect their presence. If left untreated in the ground, they can taint fresh water sources. Common DNAPLs include chlorinated hydrocarbon compounds such as carbon tetrachloride, chloroform, tetrachloroethylene, and trichloroethylene. Trichloroethylene was used during the early days of the Space Program, as a solvent for flushing rocket engines, and for metal cleaning and degreasing of equipment, electronics, and heavy machinery. As a result, areas of Cape Canaveral s Launch Complex 34, the site of several historic Saturn rocket launches occurring from 1959 to 1968, were polluted with chlorinated DNAPLs. Through the direction and guidance of Dr. Jacqueline Quinn, an environmental engineer in the Spaceport Engineering and Technology Directorate at NASA s Kennedy Space Center, a biodegradable environmental cleanup technology was developed to reductively dechlorinate DNAPL sources in polluted water at Launch Complex 34. It was important for Kennedy to nip this problem in the bud, in light of the fact that the Space Center is also a National Wildlife Refuge, home to thousands of shorebirds, endangered sea turtles and eagles, manatees, alligators, and diverse habitats that include brackish marshes and salt water estuaries. The success in remediating this historic launch site has led to numerous commercial applications that are restoring the health of our environmental surroundings.

  14. Efficient degradation of trichloroethylene in water using persulfate activated by reduced graphene oxide-iron nanocomposite.

    PubMed

    Ahmad, Ayyaz; Gu, Xiaogang; Li, Li; Lv, Shuguang; Xu, Yisheng; Guo, Xuhong

    2015-11-01

    Graphene oxide (GO) and nano-sized zero-valent iron-reduced graphene oxide (nZVI-rGO) composite were prepared. The GO and nZVI-rGO composite were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), energy-dispersive spectroscopy (EDS), and Raman spectroscopy. The size of nZVI was about 6 nm as observed by TEM. The system of nZVI-rGO and persulfate (PS) was used for the degradation of trichloroethylene (TCE) in water, and showed 26.5% more efficiency as compared to nZVI/PS system. The different parameters were studied to determine the efficiency of nZVI-rGO to activate the PS system for the TCE degradation. By increasing the PS amount, TCE removal was also improved while no obvious effect was observed by varying the catalyst loading. Degradation was decreased as the TCE initial concentration was increased from 20 to 100 mg/L. Moreover, when initial solution pH was increased, efficiency deteriorated to 80%. Bicarbonate showed more negative effect on TCE removal among the solution matrix. To better understand the effects of radical species in the system, the scavenger tests were performed. The •SO4(-) and •O2(-) were predominant species responsible for TCE removal. The nZVI-rGO-activated PS process shows potential applications in remediation of highly toxic organic contaminants such as TCE present in the groundwater. Graphical abstract Persulfate activated by reduced graphene oxide and nano-sized zero-valent iron composite can be used for efficient degradation of trichloroethylene (TCE) in water. PMID:26162447

  15. Precipitation of anionic emulsifier with ordinary Portland cement.

    PubMed

    Fang, Xing; Winnefeld, Frank; Lura, Pietro

    2016-10-01

    Cement has traditionally been used to accelerate bitumen emulsion breaking in cold mix asphalt and cold recycling asphalt. For cold emulsion mixtures, the mixing stability of bitumen emulsion is a crucial property, because it determines the distribution of bitumen and eventually affects the microstructure and the strength development of asphalt mixtures. Recent studies have proven that the interaction between cement and emulsifiers causes the destabilization of bitumen emulsions. The objective of this study is to understand the interaction between cement particles and rosin emulsifiers. For this purpose, the Ca(2+) ions and rosin emulsifier concentration after filtration were measured to identify the interaction between cement and rosin emulsifiers. The consumed emulsifier increases linearly with the amount of added cement or CaCl2 concentration in the case of diluted rosin emulsifier solutions in which the rosin emulsifier concentration is below the CMC (critical micelle concentration). In the case of concentrated rosin emulsifier solutions (above the CMC), the rosin emulsifier concentration shows a sharp decrease when a certain amount of cement or CaCl2 is added. This study indicates that cement destabilizes anionic bitumen emulsion due to the precipitation of rosin emulsifiers caused by Ca(2+) ions which are released by early cement hydration. Further studies on precipitation behavior have shown that micelles of rosin emulsifier can complex Ca(2+) ions but do not precipitate. These findings explain why slow-setting bitumen emulsions, which contain a higher concentration of emulsifier, show better mixing stability. PMID:27376974

  16. In vitro studies on silver implanted pure iron by metal vapor vacuum arc technique.

    PubMed

    Huang, Tao; Cheng, Yan; Zheng, Yufeng

    2016-06-01

    Pure iron has been verified as a promising biodegradable metal for absorbable cardiovascular stent usage. However, the degradation rate of pure iron is too slow. To accelerate the degradation of the surface of pure iron, silver ions were implanted into pure iron by metal vapor vacuum arc (MEVVA) source at an extracted voltage of 40keV. The implanted influence was up to 2×10(17)ions/cm(2). The composition and depth profiles, corrosion behavior and biocompatibility of Ag ion implanted pure iron were investigated. The implantation depths of Ag was around 60nm. The element Ag existed as Ag2O in the outermost layer, then gradually transited to metal atoms in zero valent state with depth increase. The implantation of Ag ions accelerated the corrosion rate of pure iron matrix, and exhibited much more uniform corrosion behavior. For cytotoxicity assessment, the implantation of Ag ions slightly decreased the viability of all kinds of cell lines used in these tests. The hemolysis rate of Ag ion implanted pure iron was lower than 2%, which was acceptable, whereas the platelet adhesion tests indicated the implantation of Ag ions might increase the risk of thrombosis. PMID:26925722

  17. Formulation design for target delivery of iron nanoparticles to TCE zones

    NASA Astrophysics Data System (ADS)

    Wang, Ziheng; Acosta, Edgar

    2013-12-01

    Nanoparticles of zero-valent iron (NZVI) are effective reducing agents for some dense non-aqueous phase liquid (DNAPL) contaminants such as trichloroethylene (TCE). However, target delivery of iron nanoparticles to DNAPL zones in the aquifer remains an elusive feature for NZVI technologies. This work discusses three strategies to deliver iron nanoparticles to DNAPL zones. To this end, iron oxide nanoparticles coated with oleate (OL) ions were used as stable analogs for NZVI. The OL-coated iron oxide nanoparticles are rendered lipophilic via (a) the addition of CaCl2, (b) acidification, or (c) the addition of a cationic surfactant, benzethonium chloride (BC). Mixtures of OL and BC show promise as a target delivery strategy due to the high stability of the nanoparticles in water, and their preferential partition into TCE in batch experiments. Column tests show that while the OL-BC coated iron oxide nanoparticles remain largely mobile in TCE-free columns, a large fraction of these particles are retained in TCE-contaminated columns, confirming the effectiveness of this target delivery strategy.

  18. Carbo-Iron as improvement of the nanoiron technology: From laboratory design to the field test.

    PubMed

    Mackenzie, Katrin; Bleyl, Steffen; Kopinke, Frank-Dieter; Doose, Heidi; Bruns, Johannes

    2016-09-01

    In a first pilot-scale field test the use of Carbo-Iron® was successfully demonstrated. Carbo-Iron was developed with the goal to overcome significant shortcomings of nanoscale zero-valent iron (NZVI) for in-situ groundwater remediation. The composite material of colloidal activated carbon and embedded nanoiron structures has been tested for the remediation of a tetrachloroethene (PCE) contaminated field site in Lower Saxony, Germany. The results of the two-step field test confirmed the properties intended by its design and the particle performance achieved in the laboratory experiments. The material showed transport lengths of several metres in the field and fast PCE decomposition with no vinyl chloride formation. Extended longevity of the PCE decrease in the treated area and evidence for microbiological participation were found. Carbo-Iron is now under study in the framework of the EU-project NanoREM where its performance is being further optimized at various scales from laboratory via large-scale tank to field testing. Targeted property adjustment was successful for Carbo-Iron performance in both directions: plume treatment and source attack. PMID:26299641

  19. Mechanistic Insights into Homogeneous and Heterogeneous Asymmetric Iron Catalysis

    NASA Astrophysics Data System (ADS)

    Sonnenberg, Jessica

    Our group has been focused on replacing toxic and expensive precious metal catalysts with iron for the synthesis of enantiopure compounds for industrial applications. During an investigation into the mechanism of asymmetric transfer hydrogenation with our first generation iron-(P-N-N-P) catalysts we found substantial evidence for zero-valent iron nanoparticles coated in chiral ligand acting as the active site. Extensive experimental and computational experiments were undertaken which included NMR, DFT, reaction profile analysis, substoichiometric poisoning, electron microscope imaging, XPS and multiphasic analysis, all of which supported the fact that NPs were the active species in catalysis. Reversibility of this asymmetric reaction on the nanoparticle surface was then probed using oxidative kinetic resolution of racemic alcohols, yielding modest enantiopurity and high turnover frequencies (TOF) for a range of aromatic alcohols. Efficient dehydrogenation of ammonia-borane for hydrogen evolution and the formation of B-N oligomers was also shown using the NP system, yielding highly active systems, with a maximum TOF of 3.66 H2/s-1 . We have also begun to focus on the development of iron catalysts for asymmetric direct hydrogenation of ketones using hydrogen gas. New chiral iron-(P-N-P) catalysts were developed and shown to be quite active and selective for a wide range of substrates. Mechanistic investigations primarily using NMR and DFT indicated that a highly active trans-dihydride species was being formed during catalyst activation. Lastly, a new library of chiral P-N-P and P-NH-P ligands were developed, as well as their corresponding iron complexes, some of which show promise for the development of future generations of active asymmetric direct hydrogenation catalysts.

  20. Removal of contaminants from aqueous solution by reaction with iron surfaces

    SciTech Connect

    Qiu, S.R.; Lai, H.F.; Roberson, M.J.; Hunt, M.L.; Amrhein, C.; Giancarlo, L.C.; Flynn, G.W.; Yarmoff, J.A.

    2000-03-07

    Irrigation drainage and industrial wastewaters often contain elevated levels of toxic oxyanions and oxycations such as selenate, chromate, and uranyl. A potential remediation method is to react contaminated water with zero-valent iron, which transforms the mobile contaminants into immobile forms. In this work, iron foil was exposed to aqueous solutions containing the relevant ions, and the reacted surfaces were characterized by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM images collected in situ show that the protrusions on the foil surface associated with iron oxides are smoothed out by the reaction. XPS indicates that partially reduced Se(IV) and Cr(III) are adsorbed on the surface, while uranium is deposited as U(VI), i.e., without reduction. More Se and Cr are deposited when the atmospheric gases are removed from solution because of the elimination of a competing process in which dissolved O{sub 2} increases the thickness of the iron oxide overlayer to the point where the reduction reaction is quenched. The amount of U deposited is greatly increased when the atmospheric gases are removed because of the elimination of dissolved CO{sub 2}, which can form carbonate complexes with uranium.

  1. Effects of antioxidants and additional emulsifiers on the stability of emulsified milk fat in the photo/radical oxidation system.

    PubMed

    Yamamoto, Yukihiro; Hiyama, Shinichiro; Takase, Yoshihiko; Kadowaki, Akio; Hara, Setsuko

    2014-01-01

    The effects of antioxidants on the oxidative deterioration of emulsified oils and fats differ depending on the oxidation conditions, oils and fats used, and type of emulsifier. In this study, milk fat was emulsified to obtain water-oil (O/W) emulsion using Tween20 as emulsifier. The antioxidative effects of several antioxidants with various lipophilic properties, such as δ-tocopherol (Toc), epigallocatechin gallate (EGCg), quercetin (Qu), green tea extract (GTE), and rooibos tea extract (RTE) were investigated, the effects of additional emulsifiers such as polyglycerol and sucrose esters of fatty acids on the oxidation stability of the emulsion were also investigated. Under oxidative conditions of 30°C in 650 lx, Toc was more effective than GTE in suppressing the increase of the peroxide value (PV, meq/kg) of the emulsified milk fat. Under these oxidative conditions, the antioxidative effect of GTE was enhanced by the addition of polyglycerol and sucrose esters of fatty acids. Under the oxidative conditions at 40°C in dark with 2,2'-azobis (2-amidinopropane) dihydrochloride (AAPH) or 2,2'-azobis (2,4-dimethylvaleronitrile) (AMVN), Toc showed the most antioxidative effect on suppression of the increase of PV and anisidine value (AnV) of the emulsified milk fat. Furthermore, additional emulsifiers also showed suppressive effects on the increase of the PV and AnV of the emulsified milk fat even without any antioxidants. The effects of additional emulsifiers on the oxidative stability of O/W emulsions were enhanced with antioxidants such as Toc, EGCg, and Qu. PMID:25174675

  2. Solutions Remediate Contaminated Groundwater

    NASA Technical Reports Server (NTRS)

    2010-01-01

    During the Apollo Program, NASA workers used chlorinated solvents to clean rocket engine components at launch sites. These solvents, known as dense non-aqueous phase liquids, had contaminated launch facilities to the point of near-irreparability. Dr. Jacqueline Quinn and Dr. Kathleen Brooks Loftin of Kennedy Space Center partnered with researchers from the University of Central Florida's chemistry and engineering programs to develop technology capable of remediating the area without great cost or further environmental damage. They called the new invention Emulsified Zero-Valent Iron (EZVI). The groundwater remediation compound is cleaning up polluted areas all around the world and is, to date, NASA's most licensed technology.

  3. Role of Iron Anode Oxidation on Transformation of Chromium by Electrolysis.

    PubMed

    Sarahney, Hussam; Mao, Xuhui; Alshawabkeh, Akram N

    2012-12-30

    The potential for chemical reduction of hexavalent chromium Cr(VI) in contaminated water and formation of a stable precipitate by Zero Valent Iron (ZVI) anode electrolysis is evaluated in separated electrodes system. Oxidation of iron electrodes produces ferrous ions causing the development of a reducing environment in the anolyte, chemical reduction of Cr(VI) to Cr(III) and formation of stable iron-chromium precipitates. Cr(VI) transformation rates are dependent on the applied electric current density. Increasing the electric current increases the transformation rates; however, the process is more efficient under lower volumetric current density (for example 1.5 mA L(-1) in this study). The transformation follows a zero order rate that is dependent on the electric current density. Cr(VI) transformation occurs in the anolyte when the electrodes are separated as well as when the electrolytes (anolyte/catholyte) are mixed, as used in electrocoagulation. The study shows that the transformation occurs in the anolyte as a result of ferrous ion formation and the product is a stable Fe(15)Cr(5)(OH)(60) precipitate. PMID:23284182

  4. Role of Iron Anode Oxidation on Transformation of Chromium by Electrolysis

    PubMed Central

    Sarahney, Hussam; Mao, Xuhui; Alshawabkeh, Akram N.

    2012-01-01

    The potential for chemical reduction of hexavalent chromium Cr(VI) in contaminated water and formation of a stable precipitate by Zero Valent Iron (ZVI) anode electrolysis is evaluated in separated electrodes system. Oxidation of iron electrodes produces ferrous ions causing the development of a reducing environment in the anolyte, chemical reduction of Cr(VI) to Cr(III) and formation of stable iron-chromium precipitates. Cr(VI) transformation rates are dependent on the applied electric current density. Increasing the electric current increases the transformation rates; however, the process is more efficient under lower volumetric current density (for example 1.5 mA L−1 in this study). The transformation follows a zero order rate that is dependent on the electric current density. Cr(VI) transformation occurs in the anolyte when the electrodes are separated as well as when the electrolytes (anolyte/catholyte) are mixed, as used in electrocoagulation. The study shows that the transformation occurs in the anolyte as a result of ferrous ion formation and the product is a stable Fe15Cr5(OH)60 precipitate. PMID:23284182

  5. Antibacterial activity and cytocompatibility of titanium oxide coating modified by iron ion implantation.

    PubMed

    Tian, Yaxin; Cao, Huiliang; Qiao, Yuqin; Meng, Fanhao; Liu, Xuanyong

    2014-10-01

    In this work, zero valent iron nanoparticles (Fezero-NPs) and iron oxide nanoparticles (Feox-NPs) were synthesized at the subsurface and surface regions of titanium oxide coatings (TOCs) by plasma immersion ion implantation. This novel Fe-NPs/TOC system showed negligible iron releasing, great electron storage capability and excellent cytocompatibility in vitro. Importantly, the system showed selective antibacterial ability which can kill Staphylococcus aureus under dark conditions but has no obvious antibacterial effect against Escherichia coli. Owing to a bipolar Schottky barrier between Fezero-NPs/TOC and Fezero-NPs/Feox-NPs, electrons could be captured by the Fezero-NPs bounded at the subsurface region of the coating. This electron storage capability of the Fe-NPs/TOC system induced extracellular electron transportation and accumulation of adequate valence-band holes (h(+)) at the external side, which caused oxidation damage to S. aureus cells in the dark. No obvious biocide effect against E. coli resulted from lack of electron transfer ability between E. coli and substrate materials. This work may open up a novel and controlled strategy to design coatings of implants with antibacterial ability and cytocompatibility for medical applications. PMID:24914826

  6. Hydrogeochemical and biological processes affecting the long-term performance of an iron-based permeable reactive barrier.

    PubMed

    Zolla, Valerio; Freyria, Francesca Stefania; Sethi, Rajandrea; Di Molfetta, Antonio

    2009-01-01

    Despite the wide diffusion of zero-valent iron (Fe(0)) permeable reactive barriers (PRBs), there is still a great uncertainty about their longevity and long-term performance. The aim of this study is to investigate the biological and the hydrogeochemical processes that take place at a Fe(0) installation located in Avigliana, Italy, and to derive some general considerations about long-term performance of PRBs.The examined PRB was installed in November 2004 to remediate a chlorinated solvents plume (mainly trichloroethene and 1,2-dichloroethene). The investigation was performed during the third year of operation and included: (1) groundwater sampling and analysis for chlorinated solvents, dissolved CH(4), dissolved H(2) and major inorganic constituents; (2) Fe(0) core sampling and analysis by SEM-EDS, XRD, and FTIR spectroscopy for the organic fraction; (3) in situ permeability tests and flow field monitoring by water level measurements.The study revealed that iron passivation is negligible, as the PRB is still able to effectively treat the contaminants and to reduce their concentrations below target values. Precipitation of several inorganic compounds inside the PRB was evidenced by SEM-EDS and XRD analysis conducted on iron samples. Groundwater sampling evidenced heavy sulfate depletion and the highest reported CH(4) concentration (>5,000 microg/L) at zero-valent iron PRB sites. These are due to the intense microbial activity of sulfate-reducers and methanogens, whose proliferation was most likely stimulated by the use of a biopolymer (i.e. guar gum) as shoring fluid during the excavation of the barrier. Slug tests within the barrier evidenced an apparent hydraulic conductivity two orders of magnitude lower than the predicted value. This occurrence can be ascribed to biofouling and/or accumulation of CH(4)(g) inside the iron filings.This experience suggests that when biopolymer shoring is planned to be used, long-term column tests should be performed beforehand

  7. Optimization of soil mixing technology through metallic iron addition.

    SciTech Connect

    Moos, L. P.

    1999-01-15

    Enhanced soil mixing is a process used to remove volatile organic compounds (VOCs) from soil. In this process, also known as soil mixing with thermally enhanced soil vapor extraction, or SM/TESVE, a soil mixing apparatus breaks up and mixes a column of soil up to 9 m (30 ft) deep; simultaneously, hot air is blown through the soil. The hot air carries the VOCs to the surface where they are collected and safely disposed of. This technology is cost effective at high VOC concentrations, but it becomes cost prohibitive at low concentrations. Argonne National Laboratory-East conducted a project to evaluate ways of improving the effectiveness of this system. The project investigated the feasibility of integrating the SM/TESVE process with three soil treatment processes--soil vapor extraction, augmented indigenous biodegradation, and zero-valent iron addition. Each of these technologies was considered a polishing treatment designed to remove the contaminants left behind by enhanced soil mixing. The experiment was designed to determine if the overall VOC removal effectiveness and cost-effectiveness of the SM/TESVE process could be improved by integrating this approach with one of the polishing treatment systems.

  8. Random Phase Approximation in Surface Chemistry: Water Splitting on Iron.

    PubMed

    Karlický, František; Lazar, Petr; Dubecký, Matúš; Otyepka, Michal

    2013-08-13

    The reaction of water with zero-valent iron (anaerobic corrosion) is a complex chemical process involving physisorption and chemisorption events. We employ random phase approximation (RPA) along with gradient-corrected and hybrid density functional theory (DFT) functionals to study the reaction of water with the Fe atom and Fe(100) surface. We show that the involvement of the exact electron exchange and nonlocal correlation effects in RPA improves the description of all steps of the reaction on the Fe surface with respect to standard [meaning local density approximation (LDA) or generalized gradient approximation (GGA)] DFT methods. The reaction profile calculated by range-separated hybrid functional HSE06 agrees reasonably well with the RPA profile, which makes HSE06 a computationally less demanding alternative to RPA. We also investigate the reaction of the Fe atom with water using DFT, RPA, and coupled-cluster through the perturbative triples complete basis set [CCSD(T)-3s3p-DKH/CBS] method. Local DFT methods significantly underestimate reaction barriers, while the reaction kinetics and thermodynamics from RPA agree with the reference CCSD(T) data. Both systems, i.e., the Fe atom and Fe(100), provide the same reaction mechanism, indicating that anaerobic corrosion is a stepwise process involving one-electron steps, with the first reaction step (formation of the HFeOH intermediate) representing the rate-limiting step. PMID:26584120

  9. Fast liquid-liquid reactions: Role of emulsifiers

    SciTech Connect

    Smita, S.L.; Bhave, R.R.; Sharma, M.M.

    1983-01-01

    The effect of emulsifiers such as sodium dioctyl sulfosuccinate, sorbitan monooleate, etc., on the rate of alkaline hydrolysis of higher formate esters was studied. The extraction of these formate esters is accompanied by a fast pseudo-first-order reaction in the diffusion film. Values of effective interfacial area were measured in a mechanically agitated contactor; the specific rate of extraction was measured in a stirred cell of known interfacial area. The effects of speed of agitation and the emulsifier concentration on the effective interfacial area were studied. Emulsifiers can increase the effective interfacial area markedly; the highest increase was by a factor of 14.

  10. Inhibition of bacterial growth by iron oxide nanoparticles with and without attached drug: Have we conquered the antibiotic resistance problem?

    NASA Astrophysics Data System (ADS)

    Armijo, Leisha M.; Jain, Priyanka; Malagodi, Angelina; Fornelli, F. Zuly; Hayat, Allison; Rivera, Antonio C.; French, Michael; Smyth, Hugh D. C.; Osiński, Marek

    2015-03-01

    Pseudomonas aeruginosa is among the top three leading causative opportunistic human pathogens, possessing one of the largest bacterial genomes and an exceptionally large proportion of regulatory genes therein. It has been known for more than a decade that the size and complexity of the P. aeruginosa genome is responsible for the adaptability and resilience of the bacteria to include its ability to resist many disinfectants and antibiotics. We have investigated the susceptibility of P. aeruginosa bacterial biofilms to iron oxide (magnetite) nanoparticles (NPs) with and without attached drug (tobramycin). We also characterized the susceptibility of zero-valent iron NPs, which are known to inactivate microbes. The particles, having an average diameter of 16 nm were capped with natural alginate, thus doubling the hydrodynamic size. Nanoparticle-drug conjugates were produced via cross-linking drug and alginate functional groups. Drug conjugates were investigated in the interest of determining dosage, during these dosage-curve experiments, NPs unbound to drug were tested in cultures as a negative control. Surprisingly, we found that the iron oxide NPs inhibited bacterial growth, and thus, biofilm formation without the addition of antibiotic drug. The inhibitory dosages of iron oxide NPs were investigated and the minimum inhibitory concentrations are presented. These findings suggest that NP-drug conjugates may overcome the antibiotic drug resistance common in P. aeruginosa infections.

  11. Environmental application of millimetre-scale sponge iron (s-Fe(0)) particles (III): The effect of surface silver.

    PubMed

    Ju, Yongming; Yu, Yunjiang; Wang, Xiaoyan; Zhang, Sukun; Liu, Runlong; Fu, Jianping; Han, Jinglei; Fang, Jiande; Dionysiou, Dionysios D

    2015-12-15

    To enhance the dechlorination reactivity of millimetric sponge iron (s-Fe(0)), a facile one-pot method was used to decorate s-Fe(0) with Ag(+) ions under ambient conditions. The results recorded by X-ray diffraction patterns, X-ray photoelectron spectra and high-resolution transmission electron microscopy demonstrated that the growth of Ag(0) was dominated primarily by (111) plane with a mean length of ∼20 nm. The roles of Ag(0) loading, catalyst dosage, particle size, initial pH and contaminant concentration were assessed during the removal of pentachlorophenol (PCP). Catalyst recyclability was also studied. The results revealed that 3-5mm s-Fe(0) particles with 5 wt% Ag(0) loading exhibited the best performance with a dose of 3.0 g per 60 mL PCP solution. In addition, the dechlorination of PCP followed two-step, pseudo-first-order reaction kinetics, and Ag(0)-s-Fe(0) was advantageous compared with bimetals of nanoscale zero-valent iron, iron power and iron flakes. The dechlorination mechanism of PCP over Ag(0)-s-Fe(0) was attributed to the surface Ag(0) decoration, which catalyzed the formation of reactive hydrogen atoms for indirect reaction, and the direct electron transfer via Fe-Ag(0) galvanic cells for direct reaction. This suggests that Ag-based bimetals of s-Fe(0) have great potential in the pretreatment of organic halogen compounds in aqueous solution. PMID:26276702

  12. Ambient iron-mediated aeration (IMA) for water reuse.

    PubMed

    Deng, Yang; Englehardt, James D; Abdul-Aziz, Samer; Bataille, Tristan; Cueto, Josenrique; De Leon, Omar; Wright, Mary E; Gardinali, Piero; Narayanan, Aarthi; Polar, Jose; Tomoyuki, Shibata

    2013-02-01

    Global water shortages caused by rapidly expanding population, escalating water consumption, and dwindling water reserves have rendered water reuse a strategically significant approach to meet current and future water demand. This study is the first to our knowledge to evaluate the technical feasibility of iron-mediated aeration (IMA), an innovative, potentially economical, holistic, oxidizing co-precipitation process operating at room temperature, atmospheric pressure, and neutral pH, for water reuse. In the IMA process, dissolved oxygen (O₂) was continuously activated by zero-valent iron (Fe⁰) to produce reactive oxygen species (ROS) at ambient pH, temperature, and pressure. Concurrently, iron sludge was generated as a result of iron corrosion. Bench-scale tests were conducted to study the performance of IMA for treatment of secondary effluent, natural surface water, and simulated contaminated water. The following removal efficiencies were achieved: 82.2% glyoxylic acid, ~100% formaldehyde as an oxidation product of glyoxylic acid, 94% of Ca²⁺ and associated alkalinity, 44% of chemical oxygen demand (COD), 26% of electrical conductivity (EC), 98% of di-n-butyl phthalate (DBP), 80% of 17β-estradiol (E2), 45% of total nitrogen (TN), 96% of total phosphorus (TP), 99.8% of total Cr, >90% of total Ni, 99% of color, 3.2 log removal of total coliform, and 2.4 log removal of E. Coli. Removal was attributed principally to chemical oxidation, precipitation, co-precipitation, coagulation, adsorption, and air stripping concurrently occurring during the IMA treatment. Results suggest that IMA is a promising treatment technology for water reuse. PMID:23232032

  13. Permeability of iron sulfide (FeS)-based materials for groundwater remediation.

    PubMed

    Henderson, Andrew D; Demond, Avery H

    2013-03-01

    Iron sulfide (FeS) has been extensively assessed as a reactive medium to remove both metals and halogenated organics from groundwater. However, to address its suitability as a material for permeable reactive barriers (PRBs), its propensity for solids and gas production, which result in reduced permeability, must be evaluated. The reduction in permeability for sands coated with FeS (as mackinawite), under the anoxic conditions often encountered at contaminated groundwater sites, was examined through column experiments and geochemical modeling under conditions of high calcium and nitrate, which have been previously shown to cause significant permeability reduction in zero-valent iron (ZVI) systems. The column experiments showed negligible production of both solids and gases. The geochemical modeling predicted a maximum reduction in permeability of 1% due to solids and about 30% due to gas formation under conditions for which a complete loss of permeability was predicted for ZVI systems. This difference in permeability reduction is driven by the differences in thermodynamic stability of ZVI and FeS in aqueous solutions. The results suggest that geochemical conditions that result in high permeability losses for ZVI systems will likely not be problematic for FeS-based reactive materials. PMID:23246668

  14. Uranium(VI) Reduction by Nanoscale Zerovalent Iron in Anoxic Batch Systems

    SciTech Connect

    Yan, Sen; Hua, Bin; Bao, Zhengyu; Yang, John; Liu, Chongxuan; Deng, Baolin

    2010-11-17

    This study investigated the influences of pH, bicarbonate, and calcium on U(VI) adsorption and reduction by synthetic nanosize zero valent iron (nano Fe0) particles under an anoxic condition. The results showed that about 87.1%, 82.7% and 78.3% of U(VI) could be reduced within 96 hours in the presence of 10 mM bicarbonate at pHs 6.92, 8.03 and 9.03, respectively